CN1243273A

CN1243273A - Development apparatus, its unit and picture formation method thereof

Info

Publication number: CN1243273A
Application number: CN99109469A
Authority: CN
Inventors: 冈本直树; 后关康秀; 嶋村正良; 藤岛健司; 齐木一纪; 大竹智
Original assignee: Canon Inc
Current assignee: Canon Inc
Priority date: 1998-04-17
Filing date: 1999-04-16
Publication date: 2000-02-02
Anticipated expiration: 2019-04-16
Also published as: DE69921223D1; EP0950928A1; KR19990083276A; KR100330554B1; CN100394319C; US6391511B1; DE69921223T2; EP0950928B1

Abstract

To provide a developer carrying body for development, developing device, image forming method and device unit with good environmental stability, so that positive charges can be fast, uniformly and stably given to a positive electrification toner, an excessive electrification of the toner, a melt sticking or contamination of the toner on a developer carrying body are hardly caused, and therefore, decrease in the image density, production of image defects and a coating failure (blotch) which are caused by the failures above described, and hardly caused, and furthermore stable images can be obtd. even when images are repeatedly produced. SOLUTION: This developer carrying body is used for carrying a positive electrification developer to develop an electrostatic latent image, and it consists of at least a base body and a resin coating layer. The resin coating layer contains (I) a binder resin, (II) a conductive fine powder, (III) spherical particles having 0.3 to 30 &mu m average particle size, and (IV) a quaternary ammonium salt compd.

Description

Developing apparatus, device unit and image forming method

The present invention relates to a kind of developing apparatus, device unit and image forming method, by described method, make the electrostatic latent image that forms on the electrostatic latent image carrier that in electronic photography, electrostatic recording or magnetic recording, uses, be developed into visual picture by using the developer that carrying is also transmitted on the developer carrier.

Known have some kinds of electronic photography methods usually.In general, copy is obtained like this: utilize various devices and photoconductive material to go up at electrostatic latent image carrier (sensitive piece) and form electrostatic latent image, then, utilization has the developer of toner to developing electrostatic latent image, it is visible that it is become, thereby the formation toner image is delivered to offset medium to toner image for example on the paper in time, acts on toner image on offset medium by heating, pressurization etc. then.

Toning system in electronic photography mainly is divided into the one-pack type development and two-component-type develops.In recent years, require electrophotographic device volume in light weight little.Thereby, because the part or the assembly of developing apparatus must have little volume, so use the developing apparatus that develops by the one-pack type developer in many cases.

More particularly, this one-pack type toning system does not require glass dust or the iron powder that carrier granular for example requires in the two-component-type toning system, thereby can make the volume of developing apparatus own little in light weight.In addition, because the concentration of toner must keep constant in the two-component-type toning system, thus a kind of device that is used to detect toner concentration required, so that the toner of aequum is provided, thereby under the situation of two-component-type toning system, this also makes the volume and weight of developing apparatus increase.On the other hand, this device is unwanted in the one-pack type toning system, thereby developing apparatus can be done small and lightly.

The so-called one-pack type toning system that utilizes the one-pack type developer for example is a kind of like this system, wherein electrostatic latent image is formed on the photosensitive drums as the latent image carrier, by as the development sleeve of developer carrier and the friction between the toner, and/or developer bed thickness regulating part by being used to regulate the toner coating amount on the developer sleeve and the friction between the toner, make toner positively charged or negative electricity as the one-pack type developer, then, by this development sleeve that is coated with the skim toner in its surface, make the toner that has the plus or minus electric charge be passed to the district of developing, district's photosensitive drums and development sleeve face with each other developing, and toner is flown out and, make electrostatic latent image become visible toner image so that develop attached on the electrostatic latent image that forms on the photosensitive drum surface.

The one-pack type developer that in this one-pack type toning system, uses, comprise contain be useful on make main by magnetic force effect and be carried on the one-pack type magnetic developing agent of the magnetic material on the developer carrier and do not contain the non-magnetic developing agent of one-pack type of magnetic material.Under latter event, the non-magnetic developing agent of one-pack type mainly is carried on the developer carrier by means of electrostatic forcing.According to the polarity of electric charge, the one-pack type developer also comprises the developer that has the toner that can fill negative electricity and has the developer that can fill the positive electricity toner.Like this, for example when developing on the OPC that maintains the electrostatic latent image that is filled negative electricity in its surface (organic photoconductor) sensitive piece, use has the developer that can fill the positive electricity toner, carry out the normal development of what is called this moment, and when carrying out so-called discharged-area development, use to have the developer that can fill the negative electricity toner.Use electronegative OPC sensitive piece widely, because they have stable performance and low price.Thereby, in printing machine and digital copier, use under many situations to have the developer that can fill the negative electricity toner, because what carry out is discharged-area development.In the analog copier that carries out normal development, use under many situations to have the developer that can fill the positive electricity toner, because what carry out is normal development.

As when developing, having the developer carrier that carries and transmit this developer function in its surface, use a kind of parts of for example producing like this, promptly metal, alloy or its composite mold are made cylindrical, and its surface carried out galvanic corrosion, sandblasts or fills processing, make it have desired surface roughness.But, when developer layer being adjusted to thin layer and being formed on the developer carrier surface when the developer carrier that uses this material to make and by developer bed thickness regulating part, be present in developer carrier surface and near a large amount of electric charge of developer acquisition thereof, make it be adsorbed on securely on the developer carrier surface by the image force effect.The chance that this makes toner-particle not have and the developer carrier generation rubs, thereby developer just can obtain the electric charge (phenomenon of a kind of being called as " charging ") of non-hope.Under this condition, the development that can not be satisfied with and transmission make image color very inhomogeneous, and look like to have many stains around string diagram.In addition, that the lip-deep toner that is attracted to developer carrier by this image force may cause point-like and may occur on the developer carrier and the spot that is called as stain attached thereto, cause that perhaps the fusion of toner is adhered to.

In recent years, seek the developer (toner) of photographic fixing at low temperatures for purpose of energy saving.In this case, also wish to form high-quality image.Realize setting at low temperatures in order to make toner, for example has a kind of such trend, promptly when producing toner, the Tg of developer (glass transformation temperature) is set to low, perhaps adds for example wax of bigger a little low-molecular-weight element of quantity or low melting point in resin glue.But, when this toner was used for image formation, because the temperature of device body raises or physical action, developer was attached on the surface of developer carrier with being easy to fusion, thereby be easy to cause and the minimizing of image color form image with white line and spot.

Japanese Unexamined Patent Publication No 1-112253 and 2-284158 disclose a kind of such scheme, wherein use the toner with little particle diameter, make picture quality improve also and can obtain meticulousr image.Yet, this toner per unit weight with small particle diameters has bigger surface area, thereby be tending towards having more electric charge from the teeth outwards, because so-called " charging " phenomenon, make toner to bond or the surface attached to developer carrier on, the toner that is fed on the developer carrier after making is difficult to be recharged.In this case, toner is easy to have uneven electric weight.This is easy on image to produce the sleeve ghost image, thereby forms uneven image in all black picture and half tone image, for example has straight line and image vaporific image.

Thisly to have the toner of excessive charge and stop toner in order to prevent solidly attached on the developer carrier, as Japanese Unexamined Patent Publication No 1-277256 and the disclosed a kind of method of 3-36570, wherein developer carrier is made of substrate and coating, and is scattered with conductive material for example carbon black or powdered graphite or kollag in coating.

Yet, may be not enough in this way iff making.For example, in the last few years, in image forming course, often used the parts that contact with sensitive piece.In this case, following difficulty may take place.As the parts that contact with sensitive piece, for example have the charging part as the charging rubber rollers, transfer such as transfer printing sponge roller, and cleaning device is as the cleaning rubber flap.When using these parts, they contacts with sensitive piece, thereby push towards sensitive piece at remaining toner on the sensitive piece or the toner quilt that has been bonded on these parts, are tending towards forming adhering to of film or fusion.

As a measure that addresses this problem, as Japanese Unexamined Patent Publication No 9-244398 and the disclosed a kind of method of 9-325616, wherein mention and for example use silicone oil by this way, make it be supported on the material that constitutes toner as fluid lubricant.As toner composition material with supported silicone oil thereon, the silica that magnetic material, pigment, charge control agent is arranged and also use as external additive, wherein any one can use separately, perhaps is used in combination according to the mode of being reported.But the material of Gou Chenging can improve release property by this way, this not only can stop film to form effectively or make and takes place less that film forms or above-mentioned fusion is adhered to, and can improve the transfer printing performance, thereby can stop by bad blank phenomenon (a kind of phenomenon that causes of transfer printing, the rectilinear picture that wherein has been transferred or the interior zone of character picture are not transferred, thereby keep white blank).Thereby, wish to make in this way.But, the toner of fluid lubricant in toner composition material upper support is easy to have too high electric weight, and thereby causes charging phenomenon easily.Especially this trend is stronger in the toner that can fill positive electricity, because the external additive that the chargeable property of toner greatly depends on the charge control agent that will be added and will be added by the outside.

Japanese Unexamined Patent Publication No 5-232793 discloses a kind of developing apparatus, comprising developer carrier, it has resinous coat as superficial layer, this resinous coat contains resin, graphite and carbon black at least, and be so constructed, make superficial layer and near have charge control agent so that control toner chargeable property.In addition, as charge control agent, can enumerate several charge control agents that comprise quaternary ammonium salt.As the resin that uses in the coating that is formed on the developer carrier, can enumerate and comprise phenol resin, several resins of polyamide and urethane resin.

Yet as wherein said, this prior art has provided an example, wherein uses having with phenol resin and develops with the toner of nigrosine as the filled negative electricity on the resin-coated developer carrier of charge control agent as resin.It not have to disclose the example that can fill the toner of positive electricity about use at all, also do not disclose at all or be taught in this case, when with which kind of be used in combination resin and charge control agent the time, how to make toner have positive triboelectric charge.

Simultaneously, in order to make positive charges a large amount of on the toner band, Japanese Unexamined Patent Publication No 7-114270 discloses and a kind ofly has been used to make the electric charge of developing electrostatic latent image that parts are provided, its at least the part on the surface have the quarternary ammonium salt compound of ad hoc structure.Wherein disclose above-claimed cpd and be used to form coating together with resin glue or molten resin composition selectively.As resin glue or molten resin composition, use styrene resin, the styrene-propene acid copolymer resin, polystyrene resin, epoxy resin and these resins be hybrid resin arbitrarily, or has the combination in any of amino resin on alkyl side chain.In the example, use be the styrene-propene acid copolymer resin.

Yet the developer carrier with this coating provides part to adhere to and to cause pollution by toner or in the fusion of run duration toner repeatedly as electric charge, thereby attempts to improve the runnability of developer carrier.In addition, according to the research of being undertaken by the inventor, using quarternary ammonium salt compound and styrene-propene acid copolymer resin combined and form under the situation of this coating on the developer carrier, quarternary ammonium salt compound exists only in it and only is dispersed under the state in the copolymer resin.Thereby as described in the comparative example that provides than the rear section in example of the present invention part, the charging performance of the coating of Xing Chenging can fill positive electricity like this, thereby it gives the scarce capacity of positive triboelectric charge for the toner that can fill positive electricity.

Therefore, the object of the present invention is to provide a kind of developing apparatus, device unit and image forming method, make when utilizing the toner that can fill positive electricity to carry out the development of electrostatic latent image, can make toner have stable positive charge performance is provided, can cause hardly that any excessive charging of toner and the fusion of toner on developer carrier adhere to or pollute, and can cause image color minimizing, defective image and defective toner coating (stain) hardly, these are to produce usually in the prior art.

Another object of the present invention is to provide a kind of developing apparatus, device unit and image forming method, even it can also can form stable image under the situation of copying image repeatedly, and can have the development of good environmental stability.

To achieve these goals, the invention provides a kind of developing apparatus, it comprises:

Be used to adorn the developer reservoir of developer;

Developer carrier is used for carrying the developer of the filled positive electricity that is installed in developer reservoir, and this developer is delivered to the district of developing; And

The developer layer regulating part is used to regulate the thickness of the developer layer that will be formed on the filled positive electricity on the developer carrier;

Wherein:

The resinous coat that developer carrier has a substrate at least and formed by resinous principle on this substrate surface;

This resinous principle contains (I) adhesive resin at least, and (II) Dao Dian fine powder (III) has the spheric grain of number average particle diameter from 0.3 μ m to 30 μ m, and the quarternary ammonium salt compound that (IV) can fill positive electricity to iron powder.

The present invention also provides a kind of device unit that is removably mounted on the image processing system critical piece; Described unit comprises:

Be used to adorn the developer reservoir of developer;

Developer bed thickness regulating part is used to regulate the thickness of the developer layer that will be formed on the filled positive electricity on the developer carrier;

Wherein:

The resinous coat that this developer carrier has a substrate at least and formed by resinous principle on this substrate surface;

The present invention also provides a kind of image forming method, may further comprise the steps:

Latent image forms step, is used for forming electrostatic latent image on the latent image bearing part; And

Development step, the developer of the filled positive electricity by utilizing developing apparatus makes developing electrostatic latent image;

Wherein:

In development step, make developing electrostatic latent image by means of developing apparatus, described developing apparatus comprises:

Be used to adorn the developer reservoir that can fill the positive electricity developer;

Developer carrier is used for carrying the developer of the filled positive electricity that is installed in developer reservoir, and this developer is delivered to the district of developing, wherein:

This resinous principle contains (I) adhesive resin at least, and (II) Dao Dian fine powder (III) has the spheric grain of number average particle diameter from 0.3 μ m to 30 μ m, and the quarternary ammonium salt compound that (IV) can fill positive electricity to iron powder; And

The developer that can fill positive electricity by the friction between the surface of itself and developer carrier by frictional electrification, make to give positive triboelectric charge, and make developing electrostatic latent image by the developer that uses the filled positive electricity that has been given positive triboelectric charge for the developer that can fill positive electricity.

Fig. 1 is a kind of synoptic diagram of developing apparatus, wherein uses to have resin-coated developer carrier and as the magnetic scraper plate of developer bed thickness regulating part.

Fig. 2 is a kind of synoptic diagram of developing apparatus, wherein uses to have resin-coated developer carrier and as the elastic scraper of developer bed thickness regulating part.

Fig. 3 is a kind of synoptic diagram of developer device, wherein uses to have resin-coated developer carrier and as the elastic scraper of developer bed thickness regulating part.

Fig. 4 is the lip-deep resin-coated synoptic diagram of expression developer carrier.

Fig. 5 is a kind of synoptic diagram of image processing system, wherein uses toning system of the present invention.

Fig. 6 is the synoptic diagram of conventional developing apparatus, and wherein developer carrier does not use resinous coat.

Fig. 7 is the schematic section of device unit one example of the present invention.

Fig. 8 is that image forming method of the present invention is applied to the calcspar in the printing machine of facsimile transmission system.

Fig. 9 explanation is used to measure the triboelectric charge electrical quantity measurement arrangement of quarternary ammonium salt compound to the charge polarity that gives iron powder.

Figure 10 explanation is used to measure the surface charge electrical quantity measurement arrangement of resin-coated charge polarity.

To describe the present invention in detail by providing preferred embodiment below.

The inventor has carried out extensive studies, so that solve the problem that above-mentioned prior art has.Found that, the developer carrier that is used to carry the developer that can fill positive electricity can and be provided at this suprabasil resinous coat by a substrate at least and constitute, and resinous coat can use the resinous principle that contains following component at least to make: (I) adhesive resin, (II) Dao Dian fine powder, (III) have the spheric grain of number average particle diameter from 0.3 μ m to 30 μ m, and the quarternary ammonium salt compound that (IV) can fill positive electricity to iron powder, like this, can solve problems of the prior art at an easy rate.Thereby the inventor has finished the present invention.

More particularly, in the middle of quarternary ammonium salt compound, can be comprised in the quarternary ammonium salt compound that iron powder fills positive electricity as film and form in the structure of specific adhesive resin of composition.This makes resinous coat itself become a kind of material that is filled negative electricity easily, thereby makes that can improve its positive charge for the developer that can fill positive electricity provides performance.In addition, still resinous coat is added the fine powder of conduction.This can not be trapped on the developer carrier surface electric charge, thereby can make toner avoid being attracted securely by the effect of minute surface power.In addition, having the spheric grain of number average particle diameter from 0.3 μ m to 30 μ m is added to this resinous coat.This can make the surfaceness of developer carrier stable, thereby realization makes the advantage of coating amount the best of the toner that carries on developer carrier, even and resin-coated surfaceness resinous coat surface is worn also seldom change, and makes and take place hardly to adhere to and the pollution that causes by the fusion of toner or toner.The adding of above-mentioned spheric grain can also produce following advantage: by means of interaction, improve biglyyer that Rapid and uniform electric charge provides the effect of effect and to can filling the electric charge control of positive electricity developer, and can also make charging performance more stable; This effect realizes especially having as described later-NH by the adhesive resin that is included in the resinous coat ₂Base ,=NH base and-the NH-chain in the specific adhesive resin of any one structure, this effect also realizes by quarternary ammonium salt compound.

According to the research of being undertaken by the inventor, except that above-mentioned, also find to use spheric grain that spheric grain especially conducts electricity and have real density and be 3g/cm ³Or following spheric grain, developer is coated on the developer carrier more equably, consequently can improve its antiwear property and environmental stability, even make it under the situation of long-time running, also can obtain the measured image of matter.Also once found partly or entirely have-NH as constituting the adhesive resin that resinous coat is used, using ₂Base ,=NH base and-the NH-chain in any one adhesive resin, make above-mentioned can the quarternary ammonium salt compound that iron powder fills positive electricity easily being included in this molecular structure, thereby make resinous coat itself become the material that is filled negative electricity easily, make its positive charge provide performance to be improved to the developer that can fill positive electricity.

Remove and have outside this specific resin-coated developer carrier, the developer that is carried on the filled positive electricity on it can be the developer of the filled positive electricity of one-pack type, it has the toner that contains the external additive that utilizes the fluid lubricant processing, and/or one-pack type can fill the developer of positive electricity, it has the toner that contains magnetic, and described magnetic has the fluid lubricant that supports on it.This can be recharged the developer that can fill positive electricity better.

As mentioned above, in the developer carrier that the present invention uses, form the developer that skim can be filled positive electricity in its surface, and this thin layer is carried thereon and is transmitted.This developer will illustrate below.

The toner of filled positive electricity that can fill the developer of positive electricity comprises that adhesive resin, detackifier, charge control agent and pigment are as main material.Usually, it is a kind of fine powder that is made of painted resinous principle, the acquisition of described resinous principle, be by to these material melting mixing, follow cooling curing, to the mix products efflorescence of gained, selectively classify then subsequently, make it have required particle size distribution so that adjust particle.

Bonding agent as the toner that is used for the filled positive electricity that the present invention uses can use known resin.

Can comprise as the bonding agent of toner, for example: styrene, cinnamic homopolymer or derivatives thereof, for example α-Jia Jibenyixi and p-chlorostyrene; Styrol copolymer, styrene-propene multipolymer for example, styrene-ethylene toluene multipolymer, styrene-ethyl propylene acid ester copolymer, styrene-butylacrylic acid ester copolymer, styrene-octyl group acrylate copolymer, styrene-dimethylaminoethyl multipolymer, styrene-methylmethacrylate copolymer, styrene-ethyl methacrylate copolymers, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl acrylate methyl base aminoethyl ester copolymer, styrene-methyl ethylene ether copolymer, styrene-methyl ethylene ketone copolymers, Styrene-Butadiene, styrene-isoprene multipolymer, styrene-maleic acid copolymer, and styrene-maleic acid ester copolymer; Polymethylmethacrylate; Poly-n-butyl methacrylate; Polyvinyl acetate; Tygon; Polypropylene; Polyvinyl butyral; Polyacrylate resin; Rosin; The rosin of modification; Terpene resin; Phenol resin; Aliphatic or aliphatic hydrocarbon resin; The fragrance petroleum resin; Paraffin; Brazil wax.These can use separately or use with the form of potpourri.

In the toner of the filled positive electricity of Shi Yonging, any pigment given below can be included in wherein as pigment in the present invention.For example, can use carbon black, melanin pigment, dim, sudan black SM, quick yellow G, benzidine yellow, pigment Huang, India first is orange, clothing is appropriate receive red, paranitraniline red, toluidine red, carmine 6B, purplish red FRR, the orange R of pigment, oil red 2G, dark red C, rhodamine FB, rhodamine B is dark red, and methyl violet B is dark red, phthalocyanine indigo plant, pigment indigo plant, bright green B, phthalocyanine green, oil yellow GG, the zapon first yellow CGG, reef island group Y963, reef island group YG, the zapon first orange RR, oil is dark red, the brown B of gold, zapon first dark red CG and oil-bound distemper OP.

When the toner of the filled positive electricity that uses in the present invention is used as the magnetic toner, in toner, add magnetic.Magnetizable material is as magnetic in the time of in being in magnetic field.Specifically, magnetic can comprise, feeromagnetic metal powder for example, iron for example, cobalt and nickel; Any of these feeromagnetic metal and other metal be aluminium for example, cobalt, copper-lead, manganese, tin, zinc, antimony, beryllium, bismuth, calcium, magnesium, caesium, tantalum, tungsten, vanadium; Iron oxide, magnetic iron ore for example, haematite and ferrite; With the magnet oxide, its inside or particle surface contain oxide, the hydrous oxid of metallic ion or oxyhydroxide, silicon ion for example, the magnesium ion of aluminium ion or this metal ion species.The quantity that this magnetic contained accounts for the 15%-70% of toner weight by weight greatly.

As mentioned above, the present invention can have better effect, particularly work as the developer that can fill positive electricity and have a kind of toner, during external additive that this toner was handled by additional useful fluid lubricant, perhaps when it has the colorant that contains such pigment, described pigment has support fluid lubricant thereon, with/or its upper support the magnetic of fluid lubricant is arranged.But be used for the external additive, pigment or the magnetic that give in toner, to use with the fluid lubricant of release property and lubricity, can comprise animal oil type lubricant, vegetables oil type lubricant, oil type lubricant and syntholube.It seems from its stable viewpoint, should use syntholube.

Syntholube can comprise, for example, silicone, as dimethyl silicone, the silicone of Methylphenylsilanone and various types of improvement; Polyol ester is as pentaerythritol ester and trihydroxymethylpropanyl ester; Polyolefins, as tygon, polypropylene, polybutylene and poly-(α-phenol); Polyethylene glycols is as polyethylene glycol and glycol polypropylene; The estersil class is as myristyl estersil and 14 octyl group estersil; Di-esters is as two-2-ethylhexyl sebacate and two-2-ethylhexyl adipate; Phosphorus ester is as trimethylphenyl phosphate and propyl phenyl phosphate; Fluorinated hydrocarbon, as polychlorotrifluoroethylene, teflon, Kynoar, polyvinyl fluoride; Polyphenylene ether, naphthenic hydrocarbon and alkyl aromatic compound.Particularly in the present invention, it seems that silicone and fluorinated hydrocarbon are preferred from the viewpoint of thermal stability and oxidation stability.

Silicone can comprise reactive silicone, for example amino modified silicone, epoxy resin modification silicone, carboxy-modified silicone, methyl alcohol modified silicone, methacrylyl modified silicone, sulfhydryl modified silicone, phenol-modified silicone and assorted functional group modification silicone; Non-reacted silicone, as polyether modified silicone, methyl styrene base modified silicone, hydroxyl modification silicone, fatty acid modified silicone, alkoxy-modified silicone and fluorine modified silicone; With direct silicone, as dimethyl silicone, benzyl silicone and methyl hydrogen silicone.

In the present invention, so use the fluid lubricant of listing above, make and partly to be discharged by the fluid lubricant that uses fluid lubricant to be supported on the particle surface of external additive, pigment or magnetic, thereby be present on the surface of toner-particle, but so as to giving the effect of release property and lubricity.Thereby, it seems that with regard to its character the effect of curable silicone oil is bad.Reaction silicone or have can being adsorbed on securely on the pigment or magnetic as the fluid lubricant Supporting Media of polar group, perhaps can become compatible with adhesive resin, thereby, according to absorption or compatible degree, they can be discharged slightly, so in some cases may be ineffective like that.According to the structure of side chain, non-reaction silicone oil also can become compatible with adhesive resin, and in some cases can be less relatively poor to toner-particle apparent motion thereby effect.Therefore, in the middle of above-mentioned material, preferably use dimethyl silicon oil, the silicone oil of fluorine modification and the hydrocarbon of fluoridizing do not have stronger absorption and yet incompatible because it has less reactivity and polarity and adhesive resin.

Any of these fluid lubricant preferably is added in the external additive, or it is supported on pigment or the magnetic, so that account for 0.1 to 7 part weight, and it is better to account for 0.2 to 5 part weight, and be taken as 100 parts to the weight of bonding agent this moment.

In the developer of the filled positive electricity of Shi Yonging, can add various types of detackifiers in the present invention.This detackifier can comprise: polyvinyl fluoride, fluororesin, fluorocarbon oil, silicone oil, low molecular weight polyethylene, low-molecular-weight polypropylene and various types of wax.

In the toner of the filled positive electricity of Shi Yonging, can comprise positive charge control agent in the present invention, be used to that toner is become and to fill positive electricity.Used in this case positive charge control agent can comprise, for example nigrosine and modified product thereof, the modification in addition of available fatty acid metal salts; The quaternary amine salt is as tributyl benzyl amine 1-hydroxyl-4-naphthol sulfonate, 4-butyl amine tetrafluoride borate, with its analog, father-in-law's salt, (color lake forms agent can comprise tungstophosphoric acid as the mordant pigment of phosphorus urn salt and these salt, phosphomolybdic acid, the tungsten phosphomolybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide and ferricyanic acid compound); The slaine of high fatty acid; Two organotin oxides, as dibutyl tin oxide, dioctyltin oxide and dicyclohexyl tin-oxide; With two organotin borides, as the dibutyl tin boride, dioctyl tin boride and dicyclohexyl tin boride; And imidazolium compounds.Any in these can use separately, also can two or more be used in combination.Among the present invention, in the middle of these compounds, what preferentially select for use is triphenylmethane compound, and imidazolium compounds and quaternary amine salt compound, its counter ion all are not halogens.

Homopolymer by the monomer of following formula (1) expression by the monomer of following formula (1) expression and the multipolymer of polymerisable monomer (for example above-mentioned styrene, acrylate or methacrylate), also can be used as positive charge control agent.In this case, this positive charge control agent also has and the identical effect of adhesive resin that is used as toner.

R wherein ₁Be H or CH ₃, R ₂And R ₃In each be alternative or irreplaceable alkyl (preferably having 1-4 carbon atom).

Toner for the filled positive electricity that is made of above-mentioned composition material that uses in the present invention in order to improve flowability, can selectively add fine powder from the outside.Operable in this case fine powder comprises the inorganic fine powder of inorganic oxide, silicon for example, aluminium, tantalum, germanium oxide and Zirconium oxide; Inorganic carbide is the carbonide of silicon and the carbonide of tantalum for example; Inorganic nitride, for example nitride of the nitride of silicon and germanium.

These inorganic fine powders can utilize organo-silicon compound or titanium coupling agent to carry out being used after the organic process to it.The organo-silicon compound of Shi Yonging can comprise in this case, for example, and silane coupling agent such as hexamethyldisilazane, trimethyl silane, trimethyl chlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyl trichlorosilane, allyldimethylcholrosilane, allyl phenyl dichlorosilane, the benzyl dimethyl chlorosilane, the bromomethyl dimethylchlorosilane, α-chloroethyl trichlorosilane, β-chloroethyl trichlorosilane, CMDMCS chloromethyl dimethyl chlorosilane, three Organosilyl mercaptan, trimethyl silicane mercaptan, three organic silicon acrylic esters, ethene dimethyl acetic acid base silane, dimethylethoxysilane, dimethyldimethoxysil,ne, diphenyl diethoxy silane, HMDO, 1,3-divinyl tetramethyl disiloxane, 1,3-diphenyl tetramethyl disiloxane, with the many siloxane of dimethyl, it has the 2-12 siloxane unit in each molecule, and each Si that is positioned in its end unit is connected to hydroxyl.

Also can use and utilize the silicone couplet not processed powder of processing that contains nitrogen-atoms and the material that obtains.Under the situation of the toner of the filled positive electricity that present embodiment uses especially in the present invention is favourable.Some examples as this treating agent, it can comprise: aminopropyl trimethoxysilane, aminopropyl triethoxysilane, the dimethyl aminopropyl trimethoxy silane, the diethyl amino propyl trimethoxy silicane, the dipropyl aminopropyl trimethoxysilane, the dibutylamine propyl trimethoxy silicane, the monobutyl aminopropyl trimethoxysilane, dioctyl aminopropyl dimethoxy silane, dibutylamine propyl group dimethoxy silane, dibutylamine propyl group mono methoxy silane, the dimethyl aminopropyl trimethoxy silane, trimethoxy silicon-γ-phenylpropyl amine, trimethoxy silicon-γ-propyl group benzyl amine, trimethoxy silicon-γ-propyl group piperidines, trimethoxy silicon-γ-propyl group morpholine and trimethoxy silicon-γ-propyl imidazole.These treating agents can use separately, perhaps use with two or more the form of potpourri, perhaps can with multiple processings in conjunction with or use after multiple processing.

Inorganic fine powder can be with for example comprising that sprinkling, organic solvent are handled and the method for aqueous solution processing utilizes above-mentioned silicone couplet to handle.Utilize normally a kind of such method of processing of spraying, in the method, pigment (inorganic fine powder) is stirred, and the solvent solution of aqueous solution or coupling agent is sprayed on the pigment that is stirred, dry under about 120-130 ℃ temperature then, anhydrate or solvent so that remove.It is a kind of like this method that organic solvent is handled, wherein coupling agent is at the organic solvent that contains the hydrolyst of being with low amounts of water (alcohol for example, benzene, halogenated hydrocarbon) dissolving in, and pigment is immersed in the solvent that obtains, filter then or push, so that it is realize Separation of Solid and Liquid, dry under about 120-130 ℃ then.It is a kind of such method that aqueous solution is handled, and wherein about 0.5% coupling agent is in water or have in the water-solvent mixture of described pH value and be hydrolyzed, and pigment is immersed in the hydrolysate that obtains, and carries out solid-liquid equally and separates drying then.

As the another kind of organic process of fine powder, can use fluid lubricant that inorganic fine powder is handled.For example, in order to stop film forming or, can preferentially to use the fine powder that utilizes silicone oil to handle in order to improve the transfer printing performance.Silicone oil as fluid lubricant generally can comprise those that represented by following formula (2), and they are preferentially selected for use.

Wherein R represents alkyl (for example methyl) or aryl, and n represents an integer.

As the silicone oil that can preferentially use in the present invention, can use 25 ℃ of following viscosity and be approximately 0.5-10000mm ²/ s is preferably in 1-1000mm ²The silicone oil of/s, it can comprise, for example methyl hydrogen silicone oil, dimethyl silicon oil, polymethylphenyl siloxane fluid, chlorophenylmethyl silicone oil, alkyl modified silicon oil, fatty acid modified silicone oil, polyoxyalkylene modified silicon oil and fluorine modified silicon oil.

Can use the silicone oil that on side chain, has nitrogen-atoms.In the present invention under the situation of the toner of the filled positive electricity of Shi Yonging, using the silicone oil that has nitrogen-atoms on side chain is especially favourable as the fluid lubricant of inorganic fine powder.This silicone oil can comprise having at least one silicone oil by the unit structure of following formula (3) or (4) expression.

R wherein ₁Represent hydrogen atom, alkyl, aryl or alkoxy; R ₂Represent alkylidene or phenylene, R ₃, R ₄Each represents hydrogen atom, alkyl or aryl; R ₅Representative contains the nitrogen of heterocyclic radical.

In above-mentioned molecular formula, alkyl, aryl, alkylidene, each can have the organic group that has nitrogen-atoms phenylene, maybe can have for example halogen of substituting group.

Utilization has the silicone oil of the modification as mentioned above of amine and can handle inorganic fine powder with following manner: inorganic fine powder is stirred consumingly, simultaneously selectively to its heating, spray the silicone oil of modification then, perhaps be evaporated and then spray with amine or its solution.In addition, inorganic fine powder is made into pulpous state, and the silicone oil with modification of amine or its solution is splashed in the slurry, and is simultaneously to its stirring, easily processed so as to making inorganic fine powder.

Any of these silicone oil can use separately or use with the form of two or more potpourris, perhaps can make up or be used after multiple processing.Above-mentioned processing can be carried out with the processing combination that utilizes silicone couplet.

Developer as the filled positive electricity that uses in the present invention, for electrostatic latent image is developed reliably, and can reach and have the excellent fine rule reproduction and the developing performance of medium tone level, preferably use the developer of the toner that contains following particle diameter and particle size distribution.Promptly preferably use these developers, its Be Controlled and be 3-12 μ m having the average weight particle diameter aspect the particle size distribution of toner, 5-10 μ m preferably, and the quantity content that wherein has the toner-particle of 4.0 μ m or littler diameter is 30% or still less, be preferably 5-20%, and the volume content with toner-particle of 12.7 μ m or bigger diameter is preferably 12.0% or still less, preferably 10.0% or still less.

If toner has the average weight particle diameter less than 3 μ m, for example then may taking place, toner disperses and image blurring difficulty, and when being used to form bar chart image or have the image-region image of high number percent, such problem may take place, promptly, the toner that is positioned on the transfer paper may so lack, so that produce low image color.On the other hand, if toner has the average weight particle diameter greater than 12 μ m, then may reduce the repeatability of point, thereby resolution is bad, perhaps in the toner transfer printing, disperse, when continuous duplicating, picture quality is further descended, even picture quality is good when beginning.

If the quantity content of toner-particle with 4 μ m or littler diameter is greater than 30%, then be easy to take place blooming, toner-particle is easy to take place gathering mutually and forms the toner piece of its diameter greater than green diameter simultaneously, thereby form coarse image and reduce resolution, or between the edge of sub-image and interior zone, form big density difference, thereby be easy to cause the image of hollow.

If the volume content of toner-particle with 12.7 μ m or bigger diameter then is easy to take place toner and disperses greater than 12.0%, make not only to hinder fine rule to reproduce, and cause the bad image of transfer printing.The latter causes in the process of transfer printing, wherein have greater than a spot of thick toner-particle of 12.7 μ m diameters by on the surface of the particle thin layer of the toner image that forms on the sensitive piece, protruding by development, thereby between sensitive piece and recording chart, form the tight contact condition of irregular rapid wear, cause the change of transfer printing condition by this toner image layer.

In the present invention, the particle size distribution of toner is measured with following manner.

The average particulate diameter of toner and particle size distribution can utilize Coulter Counter TA-II or Coulter Multisizer II (by Coulter Electronics, Inc. makes) to measure.In the present invention, use Coulter Multisizer II (by Coulter Electronics, Inc. makes) to measure.The interface of output distributed number and volume distributed median (being made by Nikkaki K.K.) links to each other with personal computer PC 9801 (being made by NEC).As a kind of electrolytic solution, use a grade sodium chloride to prepare the aqueous solution of 1% sodium chloride.For example, can use ISOTON R-II (obtaining) by CoulterScientific Japan Co..

By adding the surfactant of 0.1-5ml, preferably alkyl benzene sulfonate forms the above-mentioned electrolytic aqueous solution of 100-150ml, and the sample being measured of wanting that further adds 2-20mg is measured.Electrolytic solution to the sample that wherein suspending in ultrasonic dispersing machine carried out dispersion treatment about 1 minute to 3 minutes.By utilizing above-mentioned Coulter Multisizer, the aperture that uses 100 μ m is as its hole, measures particle diameter and is the volume and the quantity of 2 μ m or bigger toner-particle and calculate its volume distributed median and distributed number.Then by definite (using the typical value of the intermediate value of each passage) the weight average particle diameter (D4) of volume distributed median as each passage based on weight, determine the 4.0 μ m or the quantity percentage of the toner-particle of minor diameter more by distributed number, determine the percent by volume of the toner-particle of 12.7 μ m or larger diameter by volume distributed median.

In this case, when the developer of filled positive electricity that contains the toner of aforesaid small particle diameters and specific particle size distribution when use forms image, as previously mentioned, the toner of per unit weight has bigger surface area, thereby makes per unit weight have the big quantity of electric charge (mC/kg).Thereby this developer is easy to produce the sleeve ghost image, and this is because especially due to the electrification phenomenon in the environment of low temperature and low humidity.

Yet, in the present invention, use to have the resin-coated developer carrier that constitutes by the described specific resin composition in back as the developer carrier that in developing apparatus, uses.Even thereby the developer that uses the filled positive electricity of the toner contain small particle diameters and specific particle size distribution is when forming image, also the image that can form.More particularly, the electrification phenomenon that takes place in low temperature and low wet environment when using this developer can be limited, and this is because be formed on due to the electric charge that the resinous coat that contains conductive material on the developer carrier can suitably leak toner.In addition, when using this developer, under the environment of high temperature and high humidity, aspect the charging that promotes toner problem can take place.But can make that the charging of toner promotes higher by the resinous coat that constitutes the developer carrier that uses among the present invention, described resinous coat is made of the resinous principle that use contains quarternary ammonium salt compound, this quarternary ammonium salt compound can fill positive electricity to iron powder and specific adhesive resin, and has enough filled electronegativities.Thereby, even when using above-mentioned developer with the filled positive electricity that contains the toner that small particle diameters and specific dimensions distribute, in every kind of environment, comprising ambient temperature and moisture environment, low temperature and low humidity environment and hot and humid environment, can successfully use.

In the present invention, can use magnetic toner by above-mentioned formation as the one-pack type developer.In addition, non-magnetic toner can mix with a kind of carrier, so that as two-component developer, the carrier of perhaps getting along well mixes and is used as the non magnetic developer of one-pack type.

The developer carrier of the developer that is loaded with above-mentioned filled positive electricity in the present invention will describe in detail below.Fig. 4 represents an example of the developer carrier that uses in the present invention, and its operation will illustrate below.

The developer carrier of Shi Yonging has a substrate and resinous coat at least at first, in the present invention.As shown in Figure 4, the resinous coat 101 that is formed in the substrate 100 contains adhesive resin 102, fine conductive powder end 103 at least, and having the number average particle diameter is the spheric grain 104 of 0.3 μ m-30 μ m and the quarternary ammonium salt compound 105 that can fill positive electricity to iron powder.

As previously mentioned, in the middle of quarternary ammonium salt compound, can be comprised in the quarternary ammonium salt compound that iron powder fills positive electricity in the resinous coat of the developer carrier that formation uses in the present invention by following formula (5) expression.Thereby quarternary ammonium salt compound is included in the molecular structure as the adhesive resin of film formation material, and resinous coat itself makes the substrate that can be filled negative electricity easily, so that the positive charge that can improve the developer that can fill positive electricity provides performance.In addition, part or all of adhesive resin use has-NH at least ₂The base ,=the NH base and-the NH-chain in any adhesive resin make.This makes above-mentioned quarternary ammonium salt compound can more easily be combined in the molecular structure of this adhesive resin.

R wherein ₁, R ₂, R ₃, and R ₄In a kind of alkyl that can have a kind of substitutive derivative of each representative, can have a kind of aryl of substitutive derivative, perhaps can have a kind of aralkyl of substitutive derivative, and they can be same to each other or different to each other; X ^-Represent negative ion.

In above-mentioned general formula (5), as by X ^-The anionic example of expression can comprise organic sulfate ion, organic sulfonic acid salt ion, organic phosphoric acid salt ion, molybdate ion, tungstate ion and contain molybdenum atom or the heteropoly acid ion of tungsten atom.

In addition, because the fine conductive powder end is added in the resinous coat of the developer carrier that formation uses in the present invention, this makes electric charge can not be stuck on the developer carrier surface, thereby toner is not attracted securely by image force effect institute.Thereby this can limit the defective coating that can cause stain and toner bonding or fusion are adhered to.In this resinous coat, can add number average diameter is the spheric grain of 0.3 μ m-30 μ m.This can be so that the surfaceness of developer carrier be stable, thereby makes the coated weight that is carried on the toner on the developer carrier for best.In addition, in this case, especially can use the spheric grain of conduction, so as to making the toner coating on the developer carrier more even, thereby can improve the wearing quality and the environmental stability of developer carrier better, even the image that its long-time running also can be obtained.As the spheric grain of conduction, preferably use to have 3g/cm ³Or the spheric grain of following real density.

As mentioned above, that uses in the present invention has a resin-coated developer carrier by above-mentioned formation, can be used in combination with the toner that can fill positive electricity, at the described external additive that has utilized above-mentioned fluid lubricant to handle in the toner of positive electricity that fills from the outside adding, perhaps be used in combination, perhaps have the magnetic of fluid lubricant to be used in combination with its upper support with the toner that contains the filled positive electricity of pigment with supported fluid lubricant thereon.This can bring above-mentioned good effect and realize filling the good charging performance of positive electricity toner.

The resinous coat that is made of above-mentioned composition material preferably has the surfaceness that scope is 0.2-3.5 μ m, and better the roughness scope is 0.5-2.5 μ m, as JIS arithmetic center line surfaceness (Ra).If resin-coated Ra forms a undesirable fixed bed on the developer carrier surface because of image force less than 0.2 μ m then at the toner on the developer carrier.In case formation fixed bed, toner just can undercharges, the result produces unsatisfied developing performance, is easy to form defective image, stain occurs around for example inhomogeneous, the rectilinear picture and concentration reduces.If Ra is greater than 3.5 μ m, then the toner coating on developer carrier is so irregular, so that produce unsatisfied uniformity degree of image, perhaps makes the toner undercharge and causes that density reduces.

In the present invention, resin-coated center line surfaceness uses surface roughometer SE-3300H to measure (being made by Kosaka Kenkyusho), and under the condition of the speed of feed of the predetermined distance of the cut-out of 0.8mm, 8.0mm, 0.5mm/sec, measure 12 points and average.

Above-mentioned resinous coat preferably has 25 μ m or bed thickness still less, 20 μ m or still less more preferably, 4-20 μ m more preferably again.Under this thickness, can adorn uniform bed thickness easily.Bed thickness depends on the material that uses in the resinous coat, and when in substrate by weight from about 4000 to 20000mg/m ²When being formed, can adorn this bed thickness.

The following describes the resin-coated material of formation as the solvent of the developer carrier that uses among the present invention.

It in the present invention in the developer carrier of Shi Yonging, is added in resin-coated quarternary ammonium salt compound and can comprises any quarternary ammonium salt compound, as long as can fill positive electricity to iron powder.Be included in the quarternary ammonium salt compound in the molecular structure of specific adhesive resin, have and to make resinous coat have improved positive charge effect is provided the developer that can fill positive electricity.

In the present invention, quarternary ammonium salt compound is measured with following manner the charging polarity of iron powder.

Polarity to the electrification by friction of iron powder is measured by the blowing method, wherein uses commercially availabie electrification by friction measuring device (the TB-200 type is made by Toshiba Chemical Corporation), as shown in Figure 9.

At first, at 23 ℃, under the environment of relative humidity 60%, use EFV200/300 (obtaining) as carrier (iron powder) by Powder TeckCo., the potpourri for preparing by the quarternary ammonium salt compound that mixes 0.5g in the carrier of 9.5g is placed in the bottle of being made by tygon that volume is 50-100ml, manually shakes 50 times.Then, the resulting potpourri of 1.0-1.2g is placed with metal measuring vessel 42, provide 500 purpose conductive mesh 43 in the bottom of measuring vessel 42, and container is by covering with metal plate 43.Then, in suction apparatus 44 (it is made by insulating material with the part that measuring vessel 42 contacts at least), suck air, and operation control damper 46 makes to equal 250mmAq so that control the pressure of being indicated by vacuum indicator 47 by suction opening 45.In this state, air-breathing carrying out 1 minute is so that by the air-breathing quarternary ammonium salt compound of removing.Read out in the polarity of this moment, and be used as the polarity of quarternary ammonium salt compound the charging charge of iron powder by the current potential of pot 48 indications.Label 49 is represented capacitor.

In the present invention, resinous coat (having only resinous principle) is measured with following method for the charging polarity of iron powder.

The preparation of sample board:

Being used to form its charge plates wants measured resin-coated resin solution (remove conductive material for example carbon or graphite outside) to utilize rod to be coated with device (#60) to be painted on the SUS corrosion resistant plate, the wet coating that forms like this be dried or heat and form film (drying or heating-up temperature and time make that solution evaporates fully under the situation of thermoplastic resin, at resin under the situation of thermosetting resin by till crosslinked fully) thus prepare sample board.This sample board is placed a night under the state its ground connection in the environment of 23 ℃ and 60%RH.

The preparation of positive toner model particle:

The styrene/acrylic of 100 parts of weight-2-Octyl Nitrite/divinylbenzene copolymer (interpolymerization ratio: 80/17.5/2.5; Weight average molecular wt Mw:320000), the toluene liquid of 10 parts of weight, the spherical ferrite particles of the KOPIE BLUE PR (obtaining) of 2 parts of weight (solid substance concentration: by weight 10%) and 100 parts of weight (particle diameter: about 90 μ m) be added into, under 80 ℃, utilize the Nauta mixer to stir then 4 hours wherein by Clariant GmbH.The potpourri of gained is heated 1 hour under 140 ℃, so that solvent evaporates fully, thereby form resin bed on the ferrite particles surface.The particle of gained is decomposed, and simultaneously with its cool to room temperature, then with the screening of 83 purpose sieves, thereby removes block particle.The particle of gained is placed a night under the state its ground connection in the environment of 23 ℃ and 60%RH.These particles are designated as positive toner model particle 51 (Figure 10).

Measure

In the environment of 23 ℃ and 60%RH, measure charge polarity.At first, be set on the surface charge electrical quantity measurement arrangement TS-100AS (being made by chemical company of Toshiba) according to the sample board of above-mentioned preparation, as shown in figure 10, and pot 55 ground connection are made its value is 0.Positive toner model particle 51 according to above-mentioned preparation is placed in the water clock container 52.Press the positive toner model particle 51 of START switch water clock on sample board 53 with 20 seconds, and be received in the receiving vessel 54 of prior ground connection.Read the polarity of this moment by pot 55 indication, this polarity is with the charge polarity of the resin bed of doing iron powder is charged (having only resinous principle).Label 56 expression capacitors.

In the middle of the above-mentioned quarternary ammonium salt compound by formula (5) expression, that uses in the present invention can comprise following compound to the quarternary ammonium salt compound that iron powder fills positive electricity.Certainly, the present invention never is limited to these.

The compound 1 of example

The compound 2 of example

The compound 3 of example

The compound 4 of example

Mo ₈O ₂₆ ^4-

The compound 5 of example

The compound 6 of example

The compound 7 of example

The compound 8 of example

Can fill the quarternary ammonium salt compound of positive electricity as what use in the present invention to iron powder, can use the quarternary ammonium salt compound of the compound 1 to 8 of above-mentioned example, but never be limited to these, as long as it is to fill positive electricity to iron powder.Simultaneously, fluorine-containing quarternary ammonium salt compound, the compound shown in for example following example compound 9, it has the fluorine atom that electronics is had strong attractive force in molecular structure, be the compound that can fill negative electricity to iron powder.But, according to the research that the inventor carries out, this can not be well to filling the toner charging of positive electricity.

The compound 9 of example

In the developer carrier of Shi Yonging, the adhesive resin as film formation material when resinous coat is formed on the developer carrier can be an any kind in the present invention, and preferably can be to have-NH ₂Base ,=NH base and-resin of any one structure of NH-chain.Have-NH ₂The material of base can comprise, for example by R-NH ₂The primary amine of expression, or have the polyamine of this amine, and by RCO-NH ₂The primary amine of expression or have the polyamine of this amine.Have=material of NH base can comprise, for example secondary amine of representing by R=NH or polyamine with this amine, and by (RCO) ₂The secondary amine that=NH represents or have the polyamine of this amine.Have-material of NH-chain can comprise, for example, removes outside the above-mentioned polyamine and polyamide, have-polyurethanes of NHCOO-chain.

In the present invention, preferably can use the industrial synthetic resin one or several above-mentioned material or contain above-mentioned material as multipolymer that contains.In the present invention, in the middle of these materials, especially preferred phenol resin, polyamide and the urethane resin of producing under with the situation of ammonia as catalyzer that be to use is as what use in example.

In the present invention, when being used on developer carrier forming the used resinous principle of resinous coat by above-mentioned formation, this resinous coat can become and the developer with the toner that can fill positive electricity had good electric charge the material of performance is provided is that reason it be unclear that.The inventor supposes as follows:

When the quarternary ammonium salt compound (it can fill positive electricity to iron powder) that uses in the present invention when being added in the phenol resin, it is evenly dispersed in the phenol resin, and be heated and harden and form in the resin-coated process by in further combined with the structure at phenol resin at resin, make this phenol resin itself that contains above-claimed cpd become to have and can fill electronegative material.

When use in the present invention can be added in the polyamide to the quarternary ammonium salt compound that iron powder fills positive electricity the time, it is evenly dispersed in the polyamino resin, and be heated and dry and form in the resin-coated process by in further combined with the structure at polyamino resin at resin, make the polyamino resin composition itself that contains above-claimed cpd easily to charge to opposite polarity to the developer that can fill positive electricity.

When the quarternary ammonium salt compound that can fill positive electricity to iron powder that uses in the present invention is used in the urethane resin coating and is added in the urethane resin, it at first is evenly dispersed in the urethane resin, and is heated sclerosis and forms in the resin-coated process by in further combined with the structure at urethane resin at resin.In this process, the prototype structure of quarternary ammonium salt compound with positive polarity is destroyed, and and the urethane resin of quarternary ammonium salt compound combination becomes and has even and enough filled electronegativity, makes the urethane resin composition itself that contains above-claimed cpd easily to charge to opposite polarity to the developer that can fill positive electricity.

Use in the present invention can to fill the amount that the quarternary ammonium salt compound of positive electricity preferably is added into to iron powder be 1 to 100 part of weight, and be 100 parts with the weight of adhesive resin.Under the situation less than 1 part of weight, its interpolation provides performance not have what change to electric charge.If add greater than 100 parts of weight, then the dispersed variation of this compound in adhesive resin is tending towards making film strength to reduce.

Result as the broad research of being undertaken by the inventor, also have been found that, as the phenol resin that uses in the present invention, preferably use the phenol resin that uses nitrogenous compound to produce in process of production, because quarternary ammonium salt compound can be easily in conjunction with entering in the structure of phenol resin when heating and sclerosis as catalyzer.Thereby, in the present invention, this phenol resin that uses nitrogenous compound to produce in process of production with this effect as catalyzer, can be used as a kind of resin-coated material that forms on the developer carrier that is formed in, have the developing apparatus that good positive charge provides performance so as to realizing.

Preferably use the nitrogen-containing compound that is used as catalyzer in the production run of phenol resin in the present invention, it can comprise, for example, as acidic catalyst, ammonium salt, as ammonium sulfate, ammonium phosphate, Amcide Ammate, hartshorn salt, ammonium acetate and maleic acid ammonium, or amine salt; As base catalyst, ammonia and amino-compound, as dimethylamine, diethylamine, diisopropylamine, di-iso-butylmanice, diamylamine, trimethylamine, triethylamine, three-n-butylamine, triamylamine, dimethyl benzylamine, diethyl benzylamine, xylidin, diethylaniline, N, N-two-n-butylaniline, N, N-diamyl aniline, N, N-two-t-amyl aniline, the N-methylethanolamine, N-ehtylethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethyl ethanolamine, ethyldiethanolamine, n-butyl diethanolamine, two-n-butylethanolamine, triisopropanolamine, ethylenediamine, and hexamethylene tetramine; And nitrogen-containing heterocycle compound.Nitrogen-containing heterocycle compound can comprise pyridine and derivant thereof, as α-Jia Jibiding, and beta-picoline, γ-picoline, 2,4-lutidines and 2,6-lutidines; Quaternary compound; With imidazoles and derivant thereof, as glyoxal ethyline, 2,4-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 2-heptadecyl imidazoles.

The polyamide of Shi Yonging comprises for example nylon in the present invention, as nylon 6, nylon 66, NYLON610, nylon 11, nylon 12, nylon 9, nylon 13 and nylon Q2, with the multipolymer nylon that mainly constitutes by any material in these, alkyl-modified nylon of N and the alkoxy-modified nylon of N wherein anyly all can preferably use.Can also comprise that by polyamide modified various resins for example polyamide modified phenol resin and contain the resin of polyamide composition for example utilizes the epoxy resin of polyamide as rigidizer, wherein anyly all can preferably use.In the present invention, above-mentioned nylon and the main multipolymer nylon that is made of these nylon can preferably be used.

As the urethane resin that uses in the present invention, any urethane resin can preferably use, as long as they contain urethane bonds.Urethane bonds can obtain by the polyaddition that utilizes polyvalent alcohol and polyisocyanate.

Polyisocyanate as the urethane resin main material, can comprise, aromatic polyisocyanate for example, as TDI (toluene di-isocyanate (T), pure MDI (two isocyanic acid benzhydrols), polymeric MDI (two isocyanic acid polymethylene polyphenyl), TODI (two isocyanic acid tolidines) and NDI (naphthalene diisocyanate); And aliphatic polymeric isocyanate, as HMDI (two isocyanic acid hexylidenes), IPDI (two isocyanic acid isophorones), XDI (the inferior dimethylbenzene of two isocyanic acids), hydrogenation XDI (the inferior dimethylbenzene of hydrogenation two isocyanic acids) and hydrogenation MDI (two isocyanic acid dicyclohexyl methyl hydrides).

The polyvalent alcohol that reacts with above-mentioned polyisocyanate can comprise polyether glycol, as PPG (polyoxy propylene glycol), and polymerized polyalcohol, and polybutylene glycol (PTMG); Polyester polyol, as hexane diacid, polycaprolactone and polycarbonate polyol; The polyether-type modified polyalcohol is as PHD polyvalent alcohol and polyester ether polylol; Epoxide modified polyvalent alcohol; The partly-hydrolysed polyvalent alcohol of ethene-vinyl acetate copolymer (saponification EVA); And flame-proof polyol.

The following describes the number average particle diameter that has that is included in the resinous coat is the spheric grain of 0.3 μ m to 30 μ m.Comprising spheric grain in resinous coat has the following advantages: can make resin-coated surface have uniform surfaceness, even it is less simultaneously resin-coated surfaceness also to be changed after resin-coated surface is worn, and can seldom take place to adhere to the pollution that causes by the fusion of toner or toner.Adding spheric grain also has the following advantages: by means of interaction, can improve better that Rapid and uniform electric charge provides the effect of effect and to the charging control of the developer that can fill positive electricity and make charging performance stable; This effect realizes by the adhesive resin that comprises in resinous coat, especially-NH above-mentioned by having ₂Base ,=NH base and-the specific adhesive resin of any structure of NH-chain, and realize by quarternary ammonium salt compound.

In the present invention the number average particle diameter of the spheric grain that can have above-mentioned effect of Shi Yonging be 0.3 μ m to 30 μ m, best from 2 to 20 μ m.If the number average particle diameter of spheric grain is less than 0.3 μ m, then less to the uniform outer surface roughness influence on resinous coat surface, charging performance can be improved lessly, quick and uniform charging to developer may be not enough, and thereby toner charged also not enough, adhering to the pollution that causes by the fusion of toner and toner may be owing to resin-coated wearing and tearing takes place, thereby is easy to cause serious ghost image and minimizing image color.If spheric grain has the number average particle diameter greater than 30 μ m, then resinous coat can have too coarse surface, makes toner be difficult to be charged well, and causes the minimizing of resin-coated physical strength.

In developer carrier of the present invention, spheric grain preferably has 3g/cm ³Or following real density, 2.7g/cm ³Or following better, from 0.9 to 2.7g/cm ³Better, preferably from 0.9 to 2.5g/cm ³If the real density of spheric grain surpasses 3g/cm ³, then the dispersiveness of spheric grain in resinous coat is tending towards not enough, makes to be difficult to make the resinous coat surface to have uniform roughness, causes the uniform charging performance of toner deficiency and the intensity of resinous coat deficiency.Have at spheric grain under the situation of too little real density, spheric grain is tending towards and can not be dispersed in the resinous coat fully.

In the present invention, the real density of spheric grain utilizes dry density meter ACUPIC (being made by ShimadzuCorporation) to measure.

" sphere " of Shi Yonging is not limited to real sphere in the present invention, and is meant that having length breadth ratio is 1.0 to 1.5 particle.In the present invention, preferably using length breadth ratio is 1.0 to 1.2 spheric grain, and preferably uses real spheric grain.Has spheric grain greater than 1.5 length breadth ratio, it seems it is worthless from the uniform charging and the resin-coated intensity of toner, because the dispersiveness of this spheric grain in resinous coat may be lower, thereby resin-coated surfaceness also may be inhomogeneous.

In the present invention,, use the photo of the amplification of the electron microscope acquisition that utilizes 6000 times, from the photo of these amplifications, get 100 particles randomly, measure its length and width, thereby determine their length breadth ratios separately in order to measure the length breadth ratio of spheric grain.Its mean value is as length breadth ratio.

As the spheric grain that uses in the present invention, any known spheric grain can use, as long as it has the number average particle diameter of 0.3 μ m to 30 μ m, for example comprises spherical resin particle, spherical metal oxide particle and spherical carbide particle.Specifically, preferably spherical resin particle can obtain good surface roughness because add a spot of spherical resin particle in resinous coat, also can easily adorn uniform surface configuration.Operable in the present invention spherical resin particle for example can easily be obtained by suspension copolymerization or dispersion copolymerization.Certainly, the balling-up by heat or physics is handled and powder is made the resin particle that spheric grain obtains also can be used.

Preferred in the present invention spherical resin particle can comprise for example acrylic resin particle, as polyacrylate and polymethacrylate; The polyamide particle is as nylon; The polyolefin resin particle is as tygon and polypropylene; The silicone resin particle; The phenol resin particle; Urethane resin particles, the styrene resin particle; With the benzoguanamine particle.

The spherical resin particle of Shi Yonging can make it have deposition or be fixed on its lip-deep inorganic fine powder in the present invention.For example, the surface treatment that utilizes the spherical resin particle that this inorganic fine powder carries out as described below, can improve the dispersiveness of the spheric grain in the resinous coat, and improve formed resin-coated surface uniformity, resin-coated resistance to soiling, provide performance and resin-coated wearing quality the electric charge of toner.

The inorganic fine powder of Shi Yonging can comprise oxide, for example SiO herein ₂, SrTiO ₃, CeO ₂, CrO, AI ₂O ₃, ZnO and MgO; Nitride is Si for example ₃N ₄Carbonide, for example SiC; And sulfate or carbonate CaSO for example ₄, BaSO ₄And CaCO ₃These inorganic fine powders can utilize coupling agent to handle.More particularly, especially in order to change its adhering to or, can preferentially use the inorganic fine powder that utilizes coupling agent treatment to adhesive resin in order to make particle have hydrophobicity.

Coupling agent used herein comprises, for example silane coupling agent, titanium coupling agent and zirconium aluminate coupling agent.What need explanation especially is silane coupling agent, and it can comprise hexamethyldisilazane, trimethyl silane, trimethyl chlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyl trichlorosilane, allyldimethylcholrosilane, the allyl phenyl dichlorosilane, benzyl dimethyl chlorosilane, bromomethyl dimethylchlorosilane, α-chloroethyl trichlorosilane, β chloroethyl trichlorosilane, CMDMCS chloromethyl dimethyl chlorosilane, three organosilane mercaptan, the trimethyl silicane alkanethiol, three organosilane acrylate, ethene dimethyl acetic acid base silane, dimethyldiethoxysilane, dimethyldimethoxysil,ne, the diphenyl Ethoxysilane, HMDO, 1,3-divinyl tetramethyl disiloxane, 1, the many siloxane of 3-diphenyl tetramethyl disiloxane and dimethyl, its each molecule has the 2-12 siloxane unit, and is connected to hydroxyl on each Si of end unit of its each unit.

In the present invention, the spheric grain of conduction also can preferably be used as above-mentioned spheric grain.More particularly, can use and have 3g/cm ³Or the conduction spheric grain of following real density.That is, the spheric grain with electric conductivity can make electric charge be difficult to accumulate on the particle surface because of its electric conductivity.Thereby, in according to developer carrier of the present invention, comprise that in resinous coat this conduction spheric grain can make toner less adhered thereto, thereby can limit and toner contamination takes place and the toner fusion is adhered to that also toner being had excellent electric charge provides performance.

" conduction " of the spheric grain of the conduction of Shi Yonging refers to and has 10 in the present invention ⁶Ω cm or following body resistivity.In the present invention, preferably use has body resistivity from 10 ³Ω cm to 10 ^-6The conduction spheric grain of Ω cm.If this spheric grain has greater than 10 ⁶The body resistivity of Ω cm then owing to the spheric grain that the result of wearing and tearing is exposed to the resinous coat surface can be used as the core of toner contamination, thereby is easy to that toner contamination takes place and fusion is adhered to, and also may be difficult to realize fast and charging uniformly.

The body resistivity of conduction spheric grain is measured with following manner: the sample being measured particle is placed in the aluminium ring of 40mm diameter, and under 2500N by compression molded, so that utilize the body resistivity of four end probes by means of resistrivity meter LOW-RESTAR AP or HI-RESTAR IP (both is by Mitsubishi PetrochemicalEngineering Co., and Ltd. produces) the molded product of measurement.Measurement is carried out under the humidity of 20 to 25 ℃ temperature and 50 to 60%RH.

That use and that have above-mentioned performance in the present invention conduction spheric grain is preferably obtained by the method that comprises following method, but needn't be limited to these methods.

As the preferable methods in the present invention that obtains the conduction spheric grain; can comprise for example a kind of such method; in this method; spherical resin particle or middle carbon microballon are heated with fire; so as to carbonization and graphitization, thereby obtain to have the spherical carbon granule of the conductance that low-density becomes reconciled.The resin that uses in spherical resin particle can comprise, for example phenol resin, naphthalene resin, furane resin, xylene resin, divinylbenzene polymer, styrene-divinylbenzene copolymer and polyacrylonitrile.

The middle carbon microballon can be produced by the sphaerocrystal that forms in the process that is provided at the middle pitch of heating and sintering usually, so that for example tar, middle oil or quinoline wash with a large amount of solvents.

As obtaining the better method of conduction spheric grain, can comprise a kind of like this method, wherein a large amount of mesophase pitch utilizes the mechanochemistry method to be painted on the surface of spheric grain, wherein said spheric grain comprises phenol resin, naphthalene resin, furane resin, xylene resin, divinylbenzene copolymer, styrene-divinylbenzene copolymer or polyacrylonitrile, then, Tu Fu particle is heated in oxidizing atmosphere like this, then sintering in inert atmosphere or vacuum makes to be carbonized and graphitization, thereby obtains the spherical carbon granule of conduction.The spherical carbon granule of Huo Deing is better in this way, because the spherical carbon granule that obtains when convert graphite granule to can be in the part quilt of its coating crystalization more, so that improve conductance.

For the spherical carbon granule of the conduction that obtains with above-mentioned the whole bag of tricks, even utilize any method to obtain, the conductance of the spherical carbon granule of gained can be controlled to a certain degree by the condition that changes sintering, and this particle can preferentially be used for the present invention.In order to improve conductance more, the spherical carbon granule that obtains by said method can be on such degree coated selectively conducting metal and/or metal oxide, make the real density of conduction spheric grain be no more than 3g/cm ³

Another kind of method as the conduction spheric grain that obtains preferably to use in the present invention can comprise following method.

At first prepare the core granule of making by spherical resin particle.Then, the conductive fine particle that has less than the particle diameter of the core granule that obtains is mechanically mixed with proper mixture ratio, thereby conductive fine particle is passed through on the periphery of even action ground attached to core granule of van der waals power and electrostatic force.Then, the core granule surface softens the local temperature rising by for example giving mechanical impact by the core granule that adheres to conductive fine particle to above-mentioned acquisition.Like this, the core granule surface just is coated with one deck conductive fine particle, thereby obtains the spherical resin particle of conductive processing.

As core granule, preferably use to include organic compounds and have little real density spherical resin particle.Resin used herein can comprise, PMMA for example, acryl resin, polybutadiene, polystyrene resin, tygon, polypropylene, polybutadiene, or the multipolymer of any of these resin, benzoguanamine resin, phenol resin, polyamide, nylon, fluororesin, silicones, epoxy resin and vibrin.As the conductive fine particle (coating granule) that is attached in the surperficial usefulness of core granule (basic granules), preferably use the coating granule that has as 1/8 or littler average particulate diameter of basic granules diameter, so that the core granule surface is provided equably with conductive fine particle.

Also has a kind of another kind of method that is used to obtain the conduction spheric grain that can preferentially use in the present invention, it can comprise a kind of like this method, in this method, conductive fine particle is dispersed in the spherical resin particle equably, so as to obtaining to have the conduction spheric grain of the conductive fine particle that is dispersed in wherein.As making conductive fine particle be evenly dispersed in a kind of method in the spherical resin particle, can comprise for example a kind of like this method, in this method, adhesive resin and conductive fine particle are mixed, so that conductive fine particle is distributed in the adhesive resin particle, later on the products therefrom cooling is solidified, become to have the particle of given particle diameter then by efflorescence, then carry out mechanical treatment and thermal treatment, so that make spheric grain; In another approach, polymerization initiator, conductive fine particle and other adjuvant are added in the polymerisable monomer, and utilize dispersion machine that it is evenly dispersed in wherein, thereby acquisition monomeric compound, then in containing the liquid phase of dispersion stabilizer, carry out dispersin polymerization by means of stirrer, thereby provide given particle diameter, so that obtain to have the spheric grain that is dispersed in conductive fine particle wherein.

Utilize the conduction spheric grain of the conductive fine particle that wherein has dispersion of said method acquisition, further carry out mechanical mixture less than the conductive fine particle of core granule diameter with proper mixture ratio with particle diameter, make conductive fine particle pass through on the periphery of even action ground attached to spherical resin particle of van der waals power and electrostatic force, conducting electricity the surface of spheric grain then raises local temperature by for example mechanical impact to soften, feasible surface is coated with one deck conductive fine particle, thus the spherical resin particle that acquisition has high conductance.

In the present invention, the number average particle diameter of spheric grain uses laser diffraction particle size distribution analysis instrument LS-130 (being made by Coulter Co.) to measure, this instrument is connected the liquid module so that measure distributed number, calculate the number average particle diameter by described distributed number.

The involved quantity of the spheric grain of Shi Yonging is 2 parts to 20 parts by weight in the present invention, preferably from 2 parts to 80 parts, and is 100 parts with the weight of adhesive resin.If the content of resin-coated spheric grain is less than 2 parts of weight, the effect of then adding spheric grain is less.If more than 120 parts of weight, then be difficult to Roughness Surface on Control in suitable scope, and resinous coat may have so big surfaceness, so that make the developer layer on the developer carrier inhomogeneous.In addition, because the quantity of carrying developer thereon is big, so can not make developer have enough electrification by friction performances.In addition, resinous coat may have low film strength.

In developer carrier of the present invention, the resinous coat that is made of the material of said components preferably conducts electricity, so that stop developer, perhaps stop the electric charge deficiency that gives developer owing to the current surface that causes by the developer charging from developer carrier owing to charging sticks on the developer carrier.Thereby in the present invention, the fine conductive powder end is comprised in the resinous coat.Specifically, the resinous coat that forms on the developer carrier surface is preferably made like this, makes it have 10 ³Ω cm or following body resistivity are from 10 ^-2To 10 ³Ω cm is better, from 10 ^-2To 10 ²Ω cm is best.If resinous coat has greater than 10 ³The body resistivity of Ω cm then is easy to make the electric charge deficiency that gives developer, so that the image that is easy to pollute.If resinous coat has too little body resistivity, the electric charge that then gives developer may be too low, makes it obtain not enough friction electric weight, causes the minimizing of image density.

For resin-coated body resistivity is controlled in the above-mentioned scope, in resinous coat, preferably add following fine conductive powder end.This fine conductive powder end can comprise, metal powder for example, and as copper, nickel, silver and aluminium or its alloy; Metal oxide such as antimony oxide, indium oxide, tin oxide and titanium dioxide, and the fine conductive powder end of carbon, as carbon fiber, carbon black and graphite.The amount at the fine conductive powder end that is added can be according to the toning system that uses and difference.For example, when in transition is developed, using one-pack type insulation developer, can add the fine conductive powder end like this, make resinous coat have 10 ³Ω cm or following body resistivity.The content range at this fine conductive powder end can from 1 to 100 part of weight, is 100 parts with the weight of adhesive resin.

If the content at fine conductive powder end is less than 1 part of weight, then resinous coat may not have good electric conductivity.If content is greater than 100 parts of weight, then this resinous coat has low film strength, and toner has low electric weight.Thereby this content is not preferred.

As the fine conductive powder end of using in the present invention, preferably use carbon black.Specifically, preferably use the amorphous carbon of conduction,, by adding the conductance that just can obtain on a small quantity, and just can be controlled at conductance on the required degree by controlling its amount because it especially has excellent conductance.

In the present invention, resin-coated body resistivity is measured with following method: form the thick conductive coating of 7-20 μ m on the thick PET plate of 100 μ m, use is used to measure voltage drop type digital ohm meter conductive rubber and plastics and that have 4 end structures (Kawaquchi Denki Seisakusho manufacturing) and measures its resistivity, and this ohmmeter meets ASTM standard SRIS (D-991-82) and Japan rubber association criterion SRIS (2301-1969).Measurement is carried out under the environment of 20-25 ℃ and 50-60%RH.

Preferably include kollag in the resinous coat of the developer carrier that in constituting the present invention, uses.This kollag can comprise, molybdenum disulfide for example, boron nitride, mica, graphite, fluorographite, silver selenide-niobium, lime chloride-graphite, talcum, teflon, fluoropolymer such as PVDF and fatty acid metal salts such as zinc stearate, dolomol, aluminium stearate and zinc palmitate.Particularly preferably use graphite, because it has lubricity and electric conductivity.

The content range of any of these kollag is from 1 to 100 part of weight preferably, and be 100 parts with the weight of adhesive resin.If the solid lubrication agent content is less than 1 part of weight, then can not reach the purpose of adding kollag preferably, and developer may surface attached to developer carrier on, be easy to make image deterioration.If content surpasses 100 parts of weight, then may have low intensity, thereby be easy to and the developer carrier surface isolation at the lip-deep resinous coat of developer carrier.

With an example developing apparatus of the present invention is described below, comprising according to above-mentioned formation according to developer carrier of the present invention.

As shown in Figure 1, electrostatic latent image bearing part for example electronic photographic sensitive drum 1 rotates in the direction of arrow B, has the electrostatic latent image that is formed by known method on it.The cylindrical tube (substrate) 6 that is made of metal as the development sleeve 8 of developer carrier and be formed on its lip-deep resinous coat 7 and constitute.In the inside of dispenser shown in Figure 13, provide the stirring scraping blade 10 that is used to stir magnetic toner 4.Development sleeve 8 carries the magnetic toner of being supplied with by dispenser 34 as the one-pack type magnetic developing agent, and rotates in the direction of arrow A.Like this, magnetic toner 4 is transported to development sleeve 8 and photosensitive drums 1 opposed facing development district.In the inside of development sleeve 8, provide magnetic roller 5.Because and the friction between the resinous coat 7 on the development sleeve 8, magnetic toner 4 obtains to make the triboelectric charge of the developing electrostatic latent image on the photosensitive drums 1.

In order to regulate the bed thickness of the magnetic toner 4 that is transported to the district of developing, developer bed thickness regulating part (the adjusting scraping blade of being made by feeromagnetic metal) 2 extends in this manner vertically downward from developer reservoir, dispenser 3, make it towards development sleeve 8, and and development sleeve 8 between leave a gap that is approximately 200-300 μ m.Thereby, assemble at scraping blade 2 from the magnetic line of force that the magnetic pole N1 of magnetic roller 5 applies, so as on development sleeve 8, forming a thin layer of magnetic toner 4.Also can use the scraping blade of stronger blade scraping blade of adjusting power or non-magnetic to replace scraping blade 2.

Like this at the thickness of magnetic colorant 4 thin layers that form on the development sleeve 8 preferably less than at the development sleeve 8 in district and the minimum clearance D between the photosensitive drums 1 of developing.Developer carrier in the present invention is especially effective in the non-contact type developing apparatus, wherein by this toner thin layer electrostatic latent image is developed.But the developer carrier among the present invention also can be applied to the contact-type developing apparatus, and wherein the thickness of developer layer is greater than development sleeve of distinguishing in development 8 and the minimum clearance D between the photosensitive drums 1.In order to make explanation simple, be that example describes with the non-contact type developing apparatus below.

In development sleeve 8, fly out in order to make the magnetic toner 4 that is carried on it as the one-pack type magnetic developing agent, the developer bias voltage is added on it by power supply 9.When using DC voltage as the development bias voltage, the voltage with the intermediate value between the current potential of the current potential of electrostatic latent image district (can see the zone that magnetic toner 4 is attracted) and background area is added on the development sleeve 8.Simultaneously, for the density that strengthens the image that is developed or improve its gray shade scale, can apply alternating voltage to development sleeve 8, so that form the oscillating electric field that direction alternately changes in the district of developing.In this case, having the AC bias that the above-mentioned DC voltage component in the current potential intermediate value of the current potential of image-region and background area forms by superposeing one is added on the development sleeve 8.

Be called as under the situation of normal development, wherein toner attracted to the areas of high potential of the electrostatic latent image with areas of high potential and electronegative potential zone, can use the toner that can be charged to the opposite polarity polarity of electrostatic latent image.On the other hand, be called as under the situation of discharged-area development, wherein toner attracted to the electronegative potential zone of electrostatic latent image, can use to be charged to the toner identical with the polarity of electrostatic latent image.Additional disclosure, noble potential or electronegative potential refer to absolute value.In each case, magnetic toner 4 is the polarity that is used to make developing electrostatic latent image by electrostatic charging when with development sleeve 8 frictions.

Fig. 2 illustrates another embodiment of developing apparatus of the present invention.Fig. 3 also illustrates another embodiment of developing apparatus of the present invention.

Be characterised in that in Fig. 2 and the developing apparatus shown in Figure 3, by for example urethane rubber or silicone rubber material with caoutchouc elasticity, perhaps by the material with metallic elastic for example the elastic plate 11 made of bronze or stainless steel be used as the parts of magnetic toner 4 thickness that are adjusted on the development sleeve 8.In developing apparatus shown in Figure 2, this elasticity control scraping blade 11 is pressure with development sleeve 8 and contacts, and the direction of its pressure turns to identical with it.In developing apparatus shown in Figure 3, contact to be pressure with the direction of direction of rotation.In every kind of developing apparatus, on development sleeve 8, can form much thin toner layer.

Fig. 2 has identical structure with developing apparatus shown in Figure 1 with developing apparatus shown in Figure 3 basically in others.In Fig. 2 and Fig. 3, the label identical with Fig. 1 represented identical parts.

As 2 and developing apparatus shown in Figure 3, they are above-mentioned the sort of devices that form toner layer on development sleeve 8, this device is applicable to two kinds of situations, promptly uses mainly the situation of the one-pack type magnetic developing agent that is made of the magnetic toner and uses mainly the situation of the non-magnetic developing agent of one-pack type that is made of non-magnetic toner.

An example of a kind of image processing system of use developing apparatus of the present invention of example shown in Fig. 1 is described below with reference to Fig. 5.

In Fig. 5, label 206 expressions are as the rotation drum type sensitive piece of latent image bearing part.Sensitive piece 206 constitutes by the basalis of conduction for example made of aluminum with at its peripheral photographic layer that forms basically.The surface layer part of photographic layer is made of the thin toner of fluorine class of polycarbonate resin that contains charge transport material and 8% weight.In device shown in Figure 5, sensitive piece 206 is driven along being looked that by drawing its peripheral speed for example is 200mm/sec. along the clockwise rotation.

Label 212 is represented charging roller, a kind of contact charging parts, and as main charging device, it is made of the axle of the heart therein basically, and provides the elastic layer of the conduction of being made by the epichlorohydrin rubber that contains carbon black on its circumference.Charging roller 212 realizes that with the surface of sensitive piece 206 pressure contacts under the straight line pressure of 40g/cm, and rotates along with the rotation of sensitive piece 206.

Label 213 representative charging grid bias power supplies are used for applying voltage to charging roller 212, charging roller 212 are being applied-during the Dc bias of 1.4kV, and the surface of sensitive piece 206 is approximately by being charged to equably-polarity and the current potential of 700V.

Then, form device, on sensitive piece 206, form electrostatic latent image by image exposure 214 as latent image.The electrostatic latent image that is formed is developed by the one-pack type developer in the dispenser 201 that is contained in developing apparatus, and becomes visible toner image after developing.Label 204 is represented the transfer roll as the contact transfer, and it is made of the axle of the heart therein basically, and the elastic layer of the conduction of being made by the ethylene-propylene-butylene copolymer that contains carbon black is provided on its excircle.

Transfer roll 204 realizes that with the surface of sensitive piece 206 pressure contacts under the straight line pressure of 20g/cm, and with the speed rotation identical with the peripheral speed of sensitive piece 206.

When service recorder medium 207 for example during the paper of A4, this recording medium 207 is fed so that be installed between sensitive piece 206 and the transfer roll 204, simultaneously by transfer bias power supply 205 apply with the polarity opposite polarity of toner-the 5kV Dc bias, thereby the toner image that is formed on the sensitive piece 206 is transferred on the surface of recording medium 207.Thereby in transfer printing, transfer roll 204 realizes that with sensitive piece 206 pressure contacts by recording medium 207.

Then, being transferred toner record images medium 207 is transported on the photographic fixing assembly 208 as fixing device, its fixing roller 208a that has a halogen heater by inside basically with realize that with it resilient material pressure roll 208b that contacts constitutes under pressure, and between fixing roller 208a and pressure roll 208b, pass through, so as to make toner image by photographic fixing on recording medium 207, and after this be output as the file that forms image.

After toner image is transferred, the surface of sensitive piece 206 is cleaned, so that remove the pollution of attachment removal, remaining toner after transfer printing for example, realize aforesaid operations by means of the cleaning device 210 with flexible cleaning scraping blade 209 of being made as stock by urethane rubber, cleaning device 210 is realized contacting under the straight line pressure of 25g/cm with sensitive piece 206 in opposite direction.Eliminate 211 pairs of exposure devices by means of electric charge and should further remove static in the surface.Then, image is repeatedly formed thereon.

Device unit of the present invention comprises the developing apparatus with developer carrier of the present invention shown in Figure 1, and described developing apparatus is detachably mounted on the main body of image processing system (for example duplicating machine, laser beam printer or facsimile recorder).

A kind of form as device unit, remove outside the developing apparatus shown in Figure 1, at least can also provide a component parts of from following building block, selecting with the form of a unit: cydariform latent image bearing part (photosensitive drums) 206, the cleaning device 210 that has cleaning blade 209, and as contact (roller) charging device 212 of a charging device shown in Figure 5.Wherein, any component parts of not selecting from above-mentioned group is charging device and cleaning device for example, can be set at a side of this apparatus main body.

Fig. 7 represents an example as the handle box of device unit of the present invention.In following explanation to handle box, represent the identical functions parts with identical label in the image processing system shown in Figure 5, remove outside the developing apparatus shown in Figure 1.

As shown in Figure 7, in handle box, developing apparatus and electrostatic latent image bearing part are connected to a unit as a box at least, and this handle box is so constructed, make and to be detachably mounted on the main body of image processing system (for example duplicating machine, laser printer or facsimile recorder).

In the embodiment of handle box shown in Figure 7, for example handle box 215 is as a device unit, wherein developing apparatus, cydariform electrostatic latent image bearing part (photosensitive drums) 206, have the cleaning device 210 of cleaning blade 209 and be connected to a unit with (roller) charging device 212 that contacts as a charging device.

In the present embodiment, developing apparatus is so constructed, and makes to have development scraping blade 2, and have the one-pack type developer 4 that contains the magnetic toner in the feeding container 3 as developer reservoir.When developing, between photosensitive drums 206 and development sleeve 8 by providing the development bias voltage to form described electric field, so that utilize developer 4 to carry out development step by the bias voltage feedway.In order to carry out development step preferably, the distance between photosensitive drums 206 and the development sleeve 8 is an important factors.

In these cases, described embodiment has 4 component parts: developing apparatus, and electrostatic latent image bearing part 206, cleaning device 210 and a charging device 212, they are connected to a unit as a box.As handle box, as mentioned above, developing apparatus can be used as a box and is connected to a unit at least.For example, wherein can use two component parts, i.e. developing apparatus and electrostatic latent image bearing part, perhaps 3 component parts: developing apparatus, electrostatic latent image bearing part and cleaning device; Or 3 component parts: developing apparatus, electrostatic latent image bearing part and a charging device; Perhaps add other component parts, make to be connected to a unit as a box.

The following describes an example, wherein to use the printer that is applied to facsimile recorder according to above-mentioned developer carrier of the present invention as the image forming method of the present invention of feature.In this example, light image shown in Figure 5 exposure 214 is as the exposure of the data that are used for printing reception.Fig. 8 represents an example of an image forming course in this case with the form of calcspar.

Controller 31 control image reading section 40 and printers 39.Entire controller 31 is controlled by CPU37.Be sent to other facsimile station by transmission circuit 33 from the view data of image reading section 40 outputs.The data that receive from other facsimile station are sent to printer 39 by receiving circuit 32.Described view data is stored in the video memory 36.Printer controller 38 control printers 39.Label 34 is represented phone.

The image that receives from telephone circuit 34 (from the image information of the far-end that connects by circuit) receiving circuit 32 by demodulation, then by CPU37 to image information decoding after, be stored in order in the video memory 36.Then, in case after one page image is stored in the storer 36 at least, just carry out the image note spirit of this page.CPU37 reads the image information of one page from storer 36, and the image encoded information of one page is sent to printer controller 38.Received from the printer controller 38 of the image information of one page of CPU 37 control printers 39 like this, made it write down the image information of one page.Additional disclosure, the image information of one page under CPU 37 receives in by the process of printer 39 records.

Carry out the reception and the record of image in the manner described above.

As mentioned above, the developer of filled positive electricity that has a toner that can fill positive electricity in utilization is during to developing electrostatic latent image, the present invention can fast, evenly and stably fill positive electricity to the toner that can fill positive electricity, can not cause any surcharge of the toner that can fill positive electricity, can not cause the fusion of developer carrier is adhered to or polluted, and can not cause the minimizing of image density, can not cause the bad image that under regular situation, takes place and bad toner coating (stain).

Even the present invention can also form stable image under the situation of repeatedly duplicating, and can make development have good environmental stability.

Particularly in the process of utilizing the developer to fill positive electricity to develop, when using such developer, the present invention also can realize above-mentioned good effect, described developer has the toner that contains fluid lubricant, it does not pollute sensitive piece, charging roller and transfer roll, but and have good release property, thereby can not cause any white space that occurs owing to bad transfer printing.

Embodiment

The present invention will describe by following example that provides in detail and comparative example.In the following description, " % " and " part " that appears in example and the comparative example is for weight, except as otherwise noted.

Example 1

For 100 parts magnetic particle, adding at room temperature approximately has 1000mm ²The dimethyl silicon oil of the viscosity of/s so that utilize mixing and grinding machine to handle, is supported on the particle surface of magnetic particle the dimethyl silicon oil fluid lubricant.Then, use the magnetic particle that obtains like this, produce the toner that uses in this example as follows.

100 parts of styrene-propene butyl acrylate copolymer (Tg:58 ℃)

75 parts of the magnetic toners that the aforesaid liquid lubricant is handled

2 parts of triphenylmethane compounds (charging control agent)

4 parts in hydro carbons paraffin

Above-mentioned material utilizes the Henschel mixer to mix, and the gained potpourri is melted and stirs and use the diffusion of mariages thick stick squeezer.The mix products of gained is cooled, carry out fine-powdered by the efflorescence machine that utilizes jet then, then use the air classifier classification, thereby acquisition black toner, the weight average particle diameter that has 7.5 μ m in its particle size distribution, diameter is that the quantitative proportion of 4 μ m or littler particle is 15.5%, and diameter is that 12.7 μ m or bigger particle account for 1.0% of weight.Then, add 0.9 part fine silica powder end from the outside, it has and is approximately 1.3 * 10 ⁵m ²The BET special surface zone of/kg utilizes the amino modified silicone oil of 830 ammonia equivalent weights to handle, and mixes by the black toner of Henschel mixer and 100 parts of weight, thereby obtains the outside toner that adds silicon.This toner is used as the magnetic developing agent 1 that one-pack type can fill positive electricity.

Then, prepare the coating fluid that on the surface of development sleeve, is used for forming the electroconductive resin coating in this example by following mode.At first, the quarternary ammonium salt compound of being represented by following molecular formula (1) is used as charging control agent.On this quarternary ammonium salt compound (1), utilize the blowing method to use the polarity of triboelectric charge electrical quantity measurement arrangement TB-200 type (manufacturing of chemical company of Toshiba) measurement to the electrification by friction of iron powder, be positive polarity so that confirm it.

Spheric grain as conduction, use the spherical carbon granule of the conduction that obtains like this: on the phenol resin spheric grain of 100 parts number average particle diameters with 5.5 μ m, utilize automatic mortar (Ishikawa kojo manufacturing), evenly the number average particle diameter of 14 parts of coatings is the middle asphalt powder of the bulk of 1.5 μ m or littler coal, and the particle of coating carried out heat stabilisation process in oxidizing atmosphere, then under 2200 ℃, carry out sintering and make its graphitization.The spherical carbon granule of Huo Deing has the number average particle diameter of 5 μ m, 1.5g/cm like this ³Real density, 7.5 * 10 ^-2The body resistivity of Ω cm and 1.15 length breadth ratio.(solids content: 50%) 185 parts (as shown in table 1, P/B/CA/R compares the 20 parts of methyl alcohol of spherical carbon granule that are 5 μ m as 36 parts of (1) 30 part of number average particle diameters by above-mentioned acquisition of quarternary ammonium salt compound of being represented by above molecular formula of 4 parts of crystalline graphite of 200 parts of carbon blacks of catalyzer the phenol resin intermediate product of producing under the situation that ammonia exists: 1/2.5/0.75/0.5; CB/GF ratio: 1/9)

Then, use the sand muller above-mentioned material to be disperseed by following mode.At first, add carbon black and crystalline graphite, disperse to use beaded glass to carry out sand milling as medium for the part of the methanol solution of the intermediate product of phenol resin.For the dispersion thing that obtains, the methanol solution and the number average particle diameter that add the remaining phenol resin intermediate product that wherein is dispersed with quarternary ammonium salt compound are the spherical carbon granule of 5 μ m, so that use sand mill to continue to disperse, thereby obtain to have the coating fluid of 40% solids content.

The coating fluid utilization rod of Huo Deing is coated with device and is applied on the insulcrete like this, then heat and harden, film thereby form, be cut into standard shape then, and use low-resistivity meter LOW-RESTAR (manufacturing of Mitsubishi yuka company) to measure its body resistivity, trying to achieve its body resistivity is 4.9 * 10 ⁰Ω cm.

Then use coating fluid, on the surface of development sleeve, form the electroconductive resin coating by above-mentioned preparation.Use the external diameter that is equipped with magnetic roller and flange made by the sus stainless steel cylindrical base as 20mm as substrate.In this substrate, use the above-mentioned coating fluid of spray gun coating, utilize hot-air drier to make wet coating drying then, and hardened 30 minutes down at 150 ℃, have the electroconductive resin coating of uniform thickness thereby form.This is used as this routine development sleeve 1.

Therefrom removed the electroconductive resin coating of carbon, graphite and spherical carbon granule in development sleeve 1 composition, carried out the electrification by friction polarity check, found that to be negative polarity for positive toner type particle.

The structure of the electroconductive resin coating of Huo Deing is as shown in table 1 like this.

Then, use one-pack type can fill the magnetic developing agent 1 of positive electricity and by development sleeve 1 duplicating image of above-mentioned acquisition so that estimate.The duplicating machine NP6035 that use is produced by CANON INC. is as the image processing system duplicating image.The general configuration of this image processing system as shown in Figure 5, it has as shown in Figure 1 developing apparatus as developing apparatus.The development sleeve 1 that makes use-case 1 carries out copying image nearly 100000 (100K) as developer carrier shown in Figure 1 1. under the environment of high temperature/high humidity (H/H) of the normal temperature/low humidity (N/L) of 24 ℃/10%RH and 30 ℃/80%RH.

Utilize evaluation result that following evaluation method and evaluation criterion carry out shown in table 2 and table 3.Estimate: evaluation method

(1) image density:

Use reflection densitometer RD918 (manufacturing of Macbeth company) to measure the black continuously density of enclosing of the 5mm diameter on test card as reflection density with 5.5% image percentage.Get mean value on 5 as image density.

(2) counter-rotating photographic fog:

Measure the reflectivity of the continuously white image-region in the suitable images, and measure the reflectivity of new transfer paper, the value of (the worst value of the reflectivity of continuously white image-region)-(the highest value of the reflectivity of new transfer paper) gained is considered to the Fog density that reverses.Use basis weight to be 127.9g/m ²Presspaper as transfer paper, and utilize TC-6DS (manufacturing of Tokyo Denshoku company) measurement of reflectivity.Measurement result is shown in table 2 and table 3.

Wherein, about the value of measuring, when carrying out visual evaluation, 1.5 or following situation be that mist almost can not be by the level of visual identity; From about situation of 2.0 to 3.0 is to identify the level of mist when carefully recognizing; 4.0 or higher situation is the level that just can discern mist by casting a glance at.3.0 or following value is be evaluated as and is in the usage range.

(3) toner charge amount (Q/S) and toner operational throughput (M/S):

The toner that carries on development sleeve is gathered by utilizing the suction of metallic cylindrical tube and cylindrical filter, and wherein the quantity of electric charge of per unit weight (Q/M) (mC/kg) and the toner weight M/S (mg/cm of per unit area ²), by the electric weight Q of the electric charge that accumulates in capacitor by metallic cylindrical tube, the area S that the weight M of the toner of being gathered and toner are sucked calculates, and is used as toner charge amount (Q/M) and toner operational throughput (M/S) respectively.The result is shown in table 2 and 3.

(4) defective image:

(straight line, inhomogeneous image have the image of stain)

For example black continuously image, half tone image and rectilinear look like to be formed, and these are checked by vision, carry out any lines on the visual observation development sleeve, wavy inhomogeneous and stain (point-like inhomogeneous), and any defective toner coating on sleeve.With reference to these, estimate in the following order.It the results are shown in table 2 and table 3.A: at all do not seeing on the image He on the sleeve.B: on sleeve, can distinguish a little, but on image, almost not see.C: when browsing several to tens paper, can distinguish for nearly one.D: can be the first lap identification half tone image of sleeve rotation or first of continuous black image.E: can recognize half tone image or continuous black image.F: the defective image about whole continuous black image can be recognized.G: also can recognize continuous white image.

(5) fragment of electroconductive resin coating (film fragment):

After every kind of environment hypograph was replicated and is estimated, development sleeve was removed, and utilized model to measure its external diameter for the laser micron instrument (being made by Magara keisoku kaihatsu k.k.) of Y-CTF.The fragment (amount of debris) of the electroconductive resin coating on development sleeve, according to the measured value of such acquisition and before copying image the measured value of development sleeve external diameter calculated.Average as the fragment (μ m) of film at 30 points, it the results are shown in table 2 and table 3.

Example 2

This routine development sleeve 2 utilizes to be produced with example 1 identical mode, the number average particle diameter that just is used to form the electroconductive resin coating is that (solids content: 50%) be changed is 12 parts to the amount of the spherical carbon granule of 5 μ m (20 parts), and uses the coating fluid of preparation like this according to 200 parts of phenol resin intermediate products.To estimate with example 1 identical mode.

The structure of electroconductive resin coating is shown in table 1, and evaluation result is shown in table 2 and table 3.

Example 3

Development sleeve 3 utilizes to be produced with example 1 identical mode, the number average particle diameter that just is used to form the electroconductive resin coating is that (solids content: 50%) be changed is 28 parts to the amount of the spherical carbon granule of 5 μ m (20 parts), and uses the coating fluid of preparation like this according to 200 parts of phenol resin intermediate products.To estimate with example 1 identical mode.

Example 4

Development sleeve 4 utilizes to be produced with example 1 identical mode, the number average particle diameter that just is used to form the electroconductive resin coating is that (solids content: 50%) be changed is 60 parts to the amount of the spherical carbon granule of 5 μ m (20 parts), and uses the coating fluid of preparation like this according to 200 parts of phenol resin intermediate products.To estimate with example 1 identical mode.

Example 5

Development sleeve 5 utilizes to be produced with example 1 identical mode, and the quarternary ammonium salt compound (1) that just wherein is used to form the electroconductive resin coating utilizes the quarternary ammonium salt compound of being represented by following molecular formula (2) to replace.To estimate with example 1 identical mode.

Additional disclosure, also the quarternary ammonium salt compound (2) that uses model to measure as the triboelectric charge electrical quantity measurement arrangement (production of chemical company of Toshiba) of TB-200 to be expressed from the next with the blowing method is to the polarity of the electrification by friction of iron powder.Found that and be positive polarity.

Example 6

Development sleeve 6 utilizes to be produced with example 2 identical modes, and the quarternary ammonium salt compound (1) that just wherein is used to form the electroconductive resin coating utilizes the quarternary ammonium salt compound (2) that uses in example 5 to replace.To estimate with example 1 identical mode.

Example 7

Development sleeve 7 utilizes to be produced with example 3 identical modes, and the quarternary ammonium salt compound (1) that just wherein is used to form the electroconductive resin coating utilizes the quarternary ammonium salt compound (2) that uses in example 5 to replace.To estimate with example 1 identical mode.

Example 8

Development sleeve 8 utilizes to be produced with example 4 identical modes, and the quarternary ammonium salt compound (1) that just wherein is used to form the electroconductive resin coating utilizes the quarternary ammonium salt compound (2) by molecular formula (2) expression to replace.To estimate with example 1 identical mode.

Example 9

Development sleeve 9 utilizes to be produced with example 1 identical mode, and the number average particle diameter that just is used to form the electroconductive resin coating is that the spherical carbon granule of 5 μ m is the spherical carbon granule replacement of 2 μ m by the number average particle diameter.To estimate with example 1 identical mode.

The number average particle diameter of Shi Yonging is that the spherical carbon granule of 2 μ m is the spherical carbon granule of conduction in this example, it is to obtain like this: on the phenol resin spheric grain of 100 parts of number average particle diameters with 2.3 μ m, the number average particle diameter that utilizes automatic mortar (being made by Ishikawa kojp) evenly to apply 14 parts is the asphalt powder of the bulk of 0.3 μ m or littler coal, and the particle of coating carried out heat stabilisation process in oxidizing atmosphere, then under 2200 ℃, carry out sintering and make its graphitization; This spherical carbon granule has 1.52g/cm ³Real density, 7.2 * 10 ^-2The body resistivity of Ω cm and 1.12 length breadth ratio.

Example 10

Development sleeve 10 utilizes to be produced with example 1 identical mode, and the number average particle diameter that just is used to form the electroconductive resin coating is that the spherical carbon granule of 5 μ m is the spherical carbon granule replacement of 20 μ m by the number average particle diameter.To estimate with example 1 identical mode.

The number average particle diameter of Shi Yonging is that the spherical carbon granule of 20 μ m is the spherical carbon granule of conduction in this example, it is to obtain like this: on the phenol resin spheric grain of 100 parts the number average particle diameters with 24 μ m, utilize automatic mortar evenly the equal particle diameter of coating 14 umbers be the asphalt powder of the bulk of 3 μ m or littler coal, and the particle of coating carried out heat stabilisation process in oxidizing atmosphere, then under 2200 ℃, carry out sintering and make its graphitization; This spherical carbon granule has 1.45g/cm ³Real density, 9.6 * 10 ^-2The body resistivity of Ω cm and 1.18 length breadth ratio.

Example 11

Development sleeve 11 utilizes to be produced with example 1 identical mode, (solids content: 50%) being changed is 5 parts and 45 parts, and uses the coating fluid of preparation like this according to 200 parts of phenol resin intermediate products respectively just wherein to be used to form the amount (4 parts) of the carbon black of electroconductive resin coating and the amount (36 parts) of crystalline graphite.To estimate with example 1 identical mode.

Example 12

Development sleeve 12 utilizes to be produced with example 1 identical mode, (solids content: 50%) being changed is 3 parts and 30 parts, and uses the coating fluid of preparation like this according to 200 parts of phenol resin intermediate products respectively just wherein to be used to form the amount (4 parts) of the carbon black of electroconductive resin coating and the amount (36 parts) of crystalline graphite.To estimate with example 1 identical mode.

Example 13

Development sleeve 13 utilizes to be produced with example 1 identical mode, and the number average particle diameter that just is used to form the electroconductive resin coating is that the spherical carbon granule of 5 μ m is the PMMA particle replacement that scribbles carbon black of 5 μ m by the number average particle diameter.To estimate with example 1 identical mode.

The number average particle diameter of Shi Yonging is that the PMMA particle that scribbles carbon black of 5 μ m is the spherical PMMA particle of conduction in this example, it is to obtain like this: on 100 parts the spherical PMMA particle with 4.8 μ m number average particle diameters, utilize mixer (Nava kikai manufacturing), apply 5 parts conductive carbon black, this spherical PMMA particle has 1.20g/cm ³Real density, 6.8 * 10 ^-1The body resistivity of Ω cm and 1.06 length breadth ratio.

Example 14

Development sleeve 14 utilizes to be produced with example 1 identical mode, and the number average particle diameter that just is used to form the electroconductive resin coating is that the spherical carbon granule of 5 μ m is the resin particle replacement that is dispersed with carbon black of 5 μ m by the number average particle diameter.To estimate with example 1 identical mode.

The number average particle diameter of Shi Yonging is that the resin particle that is dispersed with carbon black of 5 μ m is the spherical resin particle of conduction in this example, it is to obtain like this: mix following material, then efflorescence and classification, thereby obtain the electroconductive resin particle of number average particle diameter 5.3 μ m, after this utilize mixer (Nava kikai manufacturing) that it is carried out balling-up and handle; This spherical resin particle has 1.21g/cm ³Real density, the body resistivity of 5.2 Ω cm and 1.20 length breadth ratio.

100 parts of styrene-diformazan aminoethyl methacrylate-divinylbenzene copolymer (polymerization ratio: 90: 10: 0.05)

25 parts of carbon blacks

Example 15

Development sleeve 15 utilizes to be produced with example 1 identical mode, and the number average particle diameter that just is used to form the electroconductive resin coating is that the spherical carbon granule of 5 μ m is the PMMA particle replacement of 5 μ m by the number average particle diameter.To estimate with example 1 identical mode.

Example 16

Development sleeve 16 utilization is produced with example 1 identical mode, just wherein the coating fluid utilization by the coating fluid replacement with solids content of 20% of following material preparation.To estimate with example 1 identical mode.

Mainly (solids content: 20%) polyamide is 500 parts for the nylon copolymer that is made of nylon 66

4 parts of carbon blacks

36 parts of crystalline graphite

(1) 20 part of quarternary ammonium salt compound

The number average particle diameter is 20 parts of the spherical carbon granules of 5 μ m

320 parts of methyl alcohol

Example 17

Development sleeve 17 utilization is produced with example 1 identical mode, just wherein the coating fluid utilization by the coating fluid replacement with solids content of 30% of following material preparation.To estimate with example 1 identical mode.

Urethane resin (solids content: 40%) 250 parts

4 parts of carbon blacks

36 parts of crystalline graphite

(1) 20 part of quarternary ammonium salt compound

270 parts of DMF

Comparative example 1

Development sleeve 18 utilization is produced with example 1 identical mode, just is not formed on the wherein electroconductive resin coating of formation, and development sleeve utilizes the replacement of FGB sleeve, and its substrate surface utilizes particle diameter to carry out blasting treatment for the beaded glass of 300#.To estimate with example 1 identical mode.

Evaluation result is shown in table 2 and table 3.

Comparative example 2

Development sleeve 19 utilizes to be produced with example 1 identical mode, and just not using the quarternary ammonium salt compound (1) and the number average particle diameter that are used to form the electroconductive resin coating therein and are used is the spherical carbon granule of 5 μ m, and uses the coating fluid of preparation like this.To estimate with example 1 identical mode.

Comparative example 3

Development sleeve 20 utilizes to be produced with example 1 identical mode, and just not using the number average particle diameter that is used to form the electroconductive resin coating therein and is used is the spherical carbon granule of 5 μ m, and uses the coating fluid of preparation like this.To estimate with example 1 identical mode.

Comparative example 4

Development sleeve 21 utilization is produced with example 1 identical mode, just wherein is used to form the electroconductive resin coating and the number average particle diameter that is used is the spherical carbon granule replacement of the spherical carbon granule of 5 μ m by number average particle diameter 35 μ m.To estimate with example 1 identical mode.

The number average particle diameter of Shi Yonging is that the spherical carbon granule of 35 μ m is the spherical carbon granule of conduction in this example, it is to obtain like this: on 100 parts of phenol resin spheric grain with 36 μ m number average particle diameters, utilize automatic mortar (Ishikawa Kojo manufacturing), evenly the number average particle diameter of 14 parts of coatings is the asphalt powder of the bulk of 5 μ m or littler coal, and the particle of coating carried out heat stabilisation process in oxidizing atmosphere, then under 2200 ℃, carry out sintering and make its graphitization; This spherical carbon granule has 1.44g/cm ³Real density, 9.8 * 10 ^-2The body resistivity of Ω cm and 1.21 length breadth ratio.

Comparative example 5

Development sleeve 22 utilizes to be produced with example 1 identical mode, does not just use the quarternary ammonium salt compound (1) that is used to form the electroconductive resin coating therein and is used, and uses the coating fluid of preparation like this.To estimate with example 1 identical mode.

Comparative example 6

Development sleeve 23 utilizes to be produced with example 13 identical modes, does not just use the quarternary ammonium salt compound (1) that is used to form the electroconductive resin coating therein and is used, and uses the coating fluid of preparation like this.To estimate with example 1 identical mode.

Comparative example 7

Development sleeve 24 utilizes to be produced with example 14 identical modes, does not just use the quarternary ammonium salt compound (1) that is used to form the electroconductive resin coating therein and is used, and uses the coating fluid of preparation like this.To estimate with example 1 identical mode.

Comparative example 8

Development sleeve 25 utilizes to be produced with example 15 identical modes, does not just use the quarternary ammonium salt compound (1) that is used to form the electroconductive resin coating therein and is used, and uses the coating fluid of preparation like this.To estimate with example 1 identical mode.

Comparative example 9

Development sleeve 26 utilizes to be produced with example 16 identical modes, just not using the quarternary ammonium salt compound (1) and the number average particle diameter that are used to form the electroconductive resin coating therein and are used is the spherical carbon granule of 5 μ m, and uses the coating fluid of preparation like this.To estimate with example 1 identical mode.

Comparative example 10

Development sleeve 27 utilizes to be produced with example 17 identical modes, just not using the quarternary ammonium salt compound (1) and the number average particle diameter that are used to form the electroconductive resin coating therein and are used is the spherical carbon granule of 5 μ m, and uses the coating fluid of preparation like this.To estimate with example 1 identical mode.

Comparative example 11

Development sleeve 28 utilizes to be produced with example 1 identical mode, the phenol resin intermediate product that just is used to form the electroconductive resin coating therein and uses is replaced by poly methyl methacrylate, and not using use therein number average particle diameter is the spherical carbon granule of 5 μ m, and uses the coating fluid of preparation like this.To estimate with example 1 identical mode.

Comparative example 12

Development sleeve 29 utilizes to be produced with example 1 identical mode, the phenol resin intermediate product that just is used to form the electroconductive resin coating therein and uses is replaced by copolymer in cinnamic acrylic ester, and not using use therein number average particle diameter is the spherical carbon granule of 5 μ m, and uses the coating fluid of preparation like this.To estimate with example 1 identical mode.

Table 1-1

Resinous coat composition in example

Resin-coated feature

* 1 rough surface is to filling the fine conductive powder spheric grain of positive electricity

P/B/CA/R is than the friction end bonding agent quaternary ammonium salt of degree Ra bed thickness body resistivity toner

Play electric polarity GB/GF*2 resinous type particle diameter example: (μ m) (Ω cm) (μ m) 1 1/2.5/0.75/0.5 0.95 16 4.9 * 10 ⁰Negative 1/9 phenol (1) carbon, 52 1/2.5/0.75/0.3 0.78 15 6.2 * 10 ⁰Negative 1/9 phenol (1) carbon, 53 1/2.5/0.75/0.7 1.12 17 3.5 * 10 ⁰Negative 1/9 phenol (1) carbon, 54 1/2.5/0.75/1.5 1.67 18 8.8 * 10 ^-1Negative 1/9 phenol (1) carbon, 55 1/2.5/0.75/0.5 0.93 16 5.0 * 10 ⁰Negative 1/9 phenol (2) carbon, 56 1/2.5/0.75/0.3 0.77 15 6.4 * 10 ⁰Negative 1/9 phenol (2) carbon, 57 1/2.5/0.75/0.7 1.11 17 3.7 * 10 ⁰Negative 1/9 phenol (2) carbon, 58 1/2.5/0.75/1.5 1.72 18 8.9 * 10 ^-1Negative 1/9 phenol (2) carbon, 59 1/2.5/0.75/0.5 0.74 14 4.2 * 10 ⁰Negative 1/9 phenol (1) carbon, 210 1/2.5/0.75/0.5 2.26 18 5.2 * 10 ⁰Negative 1/9 phenol (1) carbon, 2011 1/2.0/0.60/0.4 1.03 16 3.9 * 10 ⁰Negative 1/9 phenol (1) carbon, 512 1/3.0/0.90/0.6 0.88 15 3.4 * 10 ¹Negative 1/9 phenol (1) carbon, 513 1/2.5/0.75/0.5 0.97 16 2.3 * 10 ¹Negative 1/9 phenol (1) carbon, 514 1/2.5/0.75/0.5 0.92 17 5.9 * 10 ¹Negative 1/9 phenol (1) is coated with carbon 515 1/2.5/0.75/0.5 0.96 17 7.2 * 10 of PMMA ¹PMMA 516 1/2.5/0.50/0.5 1.03 14 1.2 * 10 of negative 1/9 phenol (1) dispersion resin ¹Negative 1/9 polyamide (1) carbon, 517 1/2.5/0.50/0.5 1.05 15 1.4 * 10 ¹Negative 1/9 polyurethane (1) carbon 5*1) P: fine conductive powder end, B: adhesive resin, CA: quarternary ammonium salt compound, R: the ratio of carbon black (CB)/crystalline graphite (GF) spheric grain * 2)

Table 1-2

Resinous coat composition in comparative example

Resin-coated feature

Playing electric polarity GB/GF*2 resinous type particle diameter comparative example (μ m) (Ω cm) (μ m) 1 utilizes the beaded glass of the grain diameter of #300 to carry out development sleeve (Ra:0.55) 2 1/2.5/-/-0.52 9 1.7 * 10 of blasting treatment ⁰Positive 1/9 phenol does not have-3 1/2.5/0.75/-0.48 12 1.2 * 10 ¹Negative 1/9 phenol (1) does not have-4 1/2.5/0.75/0.5 3.69 19 1.8 * 10 ¹Negative 1/9 phenol (1) carbon, 355 1/2.5/-/0.5 1.03 14 9.8 * 10 ^-1Carbon-free 56 1/2.5/-of positive 1/9 phenol/0.5 1.04 14 1.1 * 10 ^-1Carbon-free 57 1/2.5/-of positive 1/9 phenol/0.5 1.07 15 2.3 * 10 ¹Positive 1/9 phenol does not have carbon 58 1/2.5/-/0.5 1.06 15 3.4 * 10 that are coated with PMMA ¹Positive 1/9 phenol does not have PMMA 59 1/2.5/-/-0.46 9 6.4 * 10 of dispersion resin ⁰Positive 1/9 polyamide does not have-10 1/2.5/-/-0.51 10 7.1 * 10 ⁰Positive 1/9 polyurethane does not have-11 1/2.5/0.75/-0.63 14 3.1 * 10 ¹Positive 1/9 PMMA (1) does not have-12 1/2.5/0.75/-0.65 13 3.5 * 10 ¹Positive 1/9 styrene/(1) nothing-

Acrylate * 1) P: fine conductive powder end, B: adhesive resin, CA: quarternary ammonium salt compound, R: the ratio of carbon black (CB)/crystalline graphite (GF) spheric grain * 2)

Table 2-1

The evaluation in the N/L environment in example

Starting stage (after the 1K) operation (after the 100K)

Image density counter-rotating photographic fog Q/M M/S (1) (2) image density counter-rotating photographic fog Q/M M/S (1) (2) film fragment

(mC/kg) (mg/cm ²) (mC/kg) (mg/m ²) ( μm ) ：1 1.35 1.9 15.7 1.13 A A 1.38 1.2 15.3 1.03 A A-3.32 1.36 1.7 15.9 1.02 A A 1.37 1.0 15.5 0.92 B A-3.43 1.34 2.0 15.4 1.25 A A 1.38 1.3 14.9 1.14 A A-3.24 1.33 2.5 14.6 1.46 B A 1.37 1.7 14.1 1.35 A A-2.95 1.36 1.9 15.6 1.14 A A 1.38 1.2 15.4 1.04 A A-3.26 1.35 1.8 16.1 1.04 A A 1.37 1.1 15.8 0.94 B A-3.47 1.35 2.1 15.5 1.24 A A 1.39 1.4 15.0 1.13 A A-3.18 1.32 2.4 14.7 1.48 B A 1.36 1.6 14.3 1.37 A A-2.89 1.35 1.7 15.8 1.06 A A 1.35 1.1 15.2 0.93 B A-3.810 1.29 2.9 13.6 1.66 C B 1.32 2.1 13.1 1.49 B B-2.611 1.34 1.8 14.5 0.98 A A 1.35 1.0 14.1 0.84 A A-4.012 1.32 2.3 16.6 0.86 B A 1.34 1.7 15.7 0.81 B A-3.013 1.32 2.1 14.7 1.10 B A 1.32 1.4 14.3 0.93 B A-4.614 1.32 2.2 14.3 1.11 B A 1.31 1.5 14.0 0.92 B A-4.715 1.29 2.6 13.8 1.09 C B 1.28 1.8 13.0 0.83 C B-4.916 1.36 1.8 15.7 1.15 A A 1.39 1.1 15.2 1.07 A A-3.317 1.35 1.9 15.6 1.16 A A 1.38 1.1 15.1 1.05 A A-3.4 ( 1 ) ： ( 2 ) ：

Table 2-2

The evaluation in the N/L environment in comparative example

Starting stage (after the 1K) operation (after the 100K)

(mC/kg) (mg/cm ²) (mC/kg) (mg/cm ²) ( μm ) ：1 1.24 3.8 7.5 0.61 E F 1.20 2.9 6.7 0.49 F G-2 1.25 3.2 7.8 0.69 D D 1.23 2.5 7.2 0.61 E E-0.93 1.35 1.8 16.3 0.83 A A 1.32 1.2 12.9 0.71 D B-6.14 1.25 3.9 9.6 2.01 D D 1.24 3.2 9.1 1.78 F E-1.95 1.26 3.0 8.1 1.11 D C 1.24 2.4 7.4 1.01 E D-1.56 1.25 3.2 8.0 1.10 D C 1.23 2.6 7.3 0.99 E D-1.87 1.25 3.3 7.9 1.08 D C 1.22 2.7 7.2 0.97 E D-2.08 1.24 3.6 7.6 1.09 D C 1.21 2.8 6.8 0.89 E E-3.99 1.23 3.4 7.0 0.66 E D 1.19 2.8 6.3 0.59 F E-0.910 1.22 3.3 7.1 0.67 E D 1.18 2.9 6.4 0.58 F E-1.211 1.08 5.6 4.1 0.72 E D 0.97 5.4 3.0 0.60 F E-8.612 1.06 5.8 4.0 0.73 E D 0.95 5.5 2.9 0.61 F E-8.9 ( 1 ) ： ( 2 ) ：

Table 3-1

The evaluation in the H/H environment in example

Starting stage (after the 1K) operation (after the 100K)

(mC/kg) (mg/cm ²) (mC/kg) (mg/cm ²) ( μm ) ：1 1.31 1.3 14.5 1.12 A A 1.33 0.8 14.0 0.99 A A-3.52 1.32 1.1 14.7 1.01 .B A 1.32 0.7 14.1 0.88 B A-3.63 1.30 1.4 14.2 1.23 A A 1.32 0.9 13.8 1.10 A A-3.44 1.29 1.9 13.4 1.44 B A 1.30 1.4 12.9 1.30 B A-3.05 1.32 1.3 14.4 1.13 A A 1.33 0.8 13.9 1.00 A A-3.46 1.31 1.2 14.9 1.03 B A 1.31 0.7 14.3 0.90 B A-3.67 1.31 1.5 14.3 1.22 A A 1.33 1.0 13.8 1.09 A A-3.38 1.28 1.8 13.5 1.46 B A 1.30 1.3 13.0 1.33 B A-3.19 1.31 1.1 14.6 1.04 C A 1.30 0.7 13.9 0.89 C A-4.110 1.26 2.3 12.4 1.63 D B 1.26 1.8 11.8 1.43 D B-2.711 1.29 1.2 13.3 0.96 C A 1.29 0.7 12.6 0.83 C A-4.312 1.30 1.7 15.1 0.85 B A 1.32 1.3 14.4 0.75 A A-3.213 1.28 1.5 13.3 1.08 C A 1.29 1.0 12.8 0.95 C A-4.814 1.28 1.6 12.9 1.09 C A 1.29 1.1 12.4 0.96 C A-4.915 1.25 2.1 12.4 1.06 D B 1.26 1.6 11.8 0.89 D B-5.116 1.32 1.2 14.6 1.14 A A 1.33 0.8 14.2 1.01 A A-3.417 1.31 1.3 14.5 1.15 A A 1.32 0.9 13.9 1.01 A A-3.6 ( 1 ) ： ( 2 ) ：

Table 3-2

The evaluation in the H/.H environment in comparative example

Starting stage (after the 1K) operation (after the 100K)

(mC/kg) (mg/cm ²) (mC/kg) (mg/cm ²) ( μm ) ：1 1.18 3.1 6.2 0.59 F E 1.15 2.4 5.6 0.46 G F-2 1.19 2.5 6.5 0.68 E C 1.16 1.8 6.0 0.56 F D-1.13 1.30 1.2 15.0 0.81 C A 1.28 0.6 11.9 0.68 D B-6.34 1.20 3.2 8.3 1.97 E C 1.17 2.5 7.8 1.75 F D-2.25 1.21 2.3 6.8 1.08 E B 1.18 1.6 6.3 0.95 F C-1.76 1.21 2.5 6.7 1.07 E B 1.18 1.8 6.2 0.94 F C-2.07 1.20 2.6 6.6 1.05 E B 1.17 1.9 6.1 0.91 F C-2.28 1.19 2.9 6.3 1.04 E C 1.15 2.2 5.7 0.87 F D-4.29 1.16 2.7 5.7 0.63 F D 1.12 2.0 5.1 0.51 G E-1.110 1.17 2.7 5.8 0.64 F D 1.13 2.0 5.3 0.49 G E-1.511 1.01 5.0 2.7 0.70 F D 0.89 4.9 2.0 0.56 G E-8.912 1.00 5.2 2.6 0.71 F D 0.88 5.0 1.9 0.57 G E-9.2 ( 1 ) ： ( 2 ) ：

Claims

1. developing apparatus comprises:

Be used to adorn the developer reservoir of developer;

Wherein:

The resinous coat that described developer carrier has a substrate at least and formed by resinous principle on this substrate surface;

Described resinous principle contains (I) adhesive resin at least, and (II) Dao Dian fine powder (III) has the spheric grain of number average particle diameter from 0.3 μ m to 30 μ m, and the quarternary ammonium salt compound that (IV) can fill positive electricity to iron powder.

2. developing apparatus according to claim 1, wherein said spheric grain have the number average particle diameter from 2 μ m to 20 μ m.

3. developing apparatus according to claim 1, wherein said spheric grain has 3g/cm ³Or following real density.

4. developing apparatus according to claim 1, wherein said spheric grain has 2.7g/cm ³Or following real density.

5. developing apparatus according to claim 1, wherein said spheric grain has from 0.9g/cm ³To 2.5g/cm ³Real density.

6. developing apparatus according to claim 1, wherein said spheric grain has from 1.0 to 1.5 length breadth ratio.

7. developing apparatus according to claim 1, wherein said spheric grain has from 1.0 to 1.2 length breadth ratio.

8. developing apparatus according to claim 1, wherein said spheric grain is a spherical resin particle.

9. developing apparatus according to claim 8, wherein said spherical resin particle utilize inorganic fine powder to carry out surface treatment.

10. developing apparatus according to claim 8, wherein said spherical resin particle utilize coupling agent to carry out surface treatment.

11. developing apparatus according to claim 1, wherein said resin particle is to have 3g/cm ³Or the conduction spheric grain of following real density.

12. developing apparatus according to claim 1, wherein said resin particle is to have 2.7g/cm ³Or the conduction spheric grain of following real density.

13. developing apparatus according to claim 1, wherein said resin particle is to have from 0.9g/cm ²To 2.5g/cm ³The conduction spheric grain of real density.

14. developing apparatus according to claim 11, wherein said conduction spheric grain has 10 ⁶Ω cm or following body resistivity.

15. developing apparatus according to claim 11, wherein said conduction spheric grain has from 10 ^-6Ω cm to 10 ³The body resistivity of Ω cm.

16. developing apparatus according to claim 11, wherein said conduction spheric grain comprises the spherical resin particle that was carbonized by sintering.

17. developing apparatus according to claim 11, wherein said conduction spheric grain comprise the spherical middle carbon microballon of being crossed by graphitization by sintering.

18. developing apparatus according to claim 11, the inside of wherein said conduction spheric grain was carbonized, and its outside is by the graphitization mistake.

19. developing apparatus according to claim 18, wherein said conduction spheric grain is the spheric grain that obtains like this: the mesophase pitch that applies bulk on the surface of spherical resin particle, the particle that heating applies in oxidizing atmosphere, sintering in inert atmosphere or vacuum then.

20. developing apparatus according to claim 11, wherein said conduction spheric grain is coated with conducting metal or conducting metal oxide, or applies with both.

21. developing apparatus according to claim 11, wherein said conduction spheric grain comprises that its surface was carried out the spheric grain of conductive processing.

22. developing apparatus according to claim 21, wherein said conduction spheric grain are the spheric grain that obtains like this: conductive fine particle is sticked on the surface of spherical resin particle, and the particle of gained is carried out mechanical impact.

23. developing apparatus according to claim 11, wherein said conduction spheric grain comprises the spherical resin particle that wherein is scattered with conductive fine particle.

24. developing apparatus according to claim 23; wherein said conduction spheric grain is the particle that obtains like this: resin and conductive fine particle are mixed; the cooling of the mix products of gained is caused curing; with the cured product efflorescence of gained, and by mechanical treatment or thermal treatment or make the efflorescence product balling-up of gained by two kinds of processing.

25. developing apparatus according to claim 1, wherein said resinous coat contains resin particle, and its amount is for from 2 parts of weight to 120 part weight, is 100 parts with the weight of adhesive resin.

26. developing apparatus according to claim 1, wherein said quarternary ammonium salt compound comprise the compound of being represented by following general molecular formula:

Wherein, R ₁, R ₂, R ₃, R ₄In each represent alkyl, it can have substitute, aryl, it can have substitute, or aralkyl, it can have substitute, and can be identical or different; And X ^-Represent negative ion.

27. developing apparatus according to claim 26, wherein said negative ion comprises select a kind of from following group: the organic sulfate ion, the organic sulfonic acid salt ion, the organic phosphoric acid salt ion, molybdate ion, tungstate ion contains the heteropoly acid ion of molybdenum atom and contains the heteropoly acid ion of tungsten atom.

28. developing apparatus according to claim 1, wherein said resinous coat contains described quarternary ammonium salt compound, and its quantity is from 1 part of weight to 100 part weight, is 100 parts with the weight of adhesive resin.

29. developing apparatus according to claim 1, wherein said adhesive resin has-NH ₂Base ,=the NH base and-in the NH-chain any one.

30. developing apparatus according to claim 29, the resin of wherein said adhesive resin for from the group that comprises following resin, selecting: phenol resin, polyamide and urethane resin.

31. developing apparatus according to claim 1, wherein said resinous coat have the center line surfaceness that scope is 0.2-3.5.

32. developing apparatus according to claim 1, the wherein said developer that fills positive electricity comprises the toner that can fill positive electricity.

33. developing apparatus according to claim 1, the wherein said developer that fills positive electricity are the one-pack type developers with the magnetic toner that can fill positive electricity.

34. developing apparatus according to claim 1, the wherein said developer that fills positive electricity are the one-pack type developers with the non-magnetic toner that can fill positive electricity.

35. developing apparatus according to claim 32, the wherein said toner that fills positive electricity comprises detackifier.

36. developing apparatus according to claim 32, the wherein said toner that fills positive electricity comprises positive charge control agent.

37. developing apparatus according to claim 1, the wherein said developer that fills positive electricity comprise toner that can fill positive electricity and the external additive that utilizes fluid lubricant to handle.

38. developing apparatus according to claim 32, the wherein said toner that fills positive electricity comprise its upper support the colorant of fluid lubricant or the magnetic powder that its upper support has fluid lubricant are arranged, perhaps have described colorant and magnetic powder.

39. developing apparatus according to claim 32, the wherein said toner that fills positive electricity has the average weight particle diameter in its particle size distribution be 3-12 μ m, and have 4.0 μ m or more the quantity content of the toner-particle of minor diameter be 30% or still less, the volume content with toner-particle of 12.7 μ m or larger diameter is 12.0% or still less.

40. developing apparatus according to claim 1, the thickness of the developer layer of the filled positive electricity that will form on described developer carrier wherein is less than the minimum clearance between the surface of the surface of described developer carrier and electrostatic latent image bearing part.

41. developing apparatus according to claim 1 is comprising the power supply that is used for providing to described developer carrier bias voltage.

42. according to the described developing apparatus of claim 41, wherein said bias voltage has the AC bias that is superimposed with DC component on it.

43. a device unit that is removably mounted on the image processing system critical piece, described unit comprises:

Be used to adorn the developer reservoir of developer;

Wherein:

Described resinous principle contains (I) adhesive resin at least, and (II) Dao Dian fine powder (III) has the spheric grain of average particulate diameter from 0.3 μ m to 30 μ m, and the quarternary ammonium salt compound that (IV) can fill positive electricity to iron powder.

44. according to the described device unit of claim 43, wherein said spheric grain has the number average particle diameter from 2 μ m to 20 μ m.

45. according to the described device unit of claim 43, wherein said spheric grain has 3g/cm ³Or following real density.

46. according to the described device unit of claim 43, wherein said spheric grain has 2.7g/cm ³Or following real density.

47. according to the described device unit of claim 43, wherein said spheric grain has from 0.9g/cm ³To 2.5g/cm ³Real density.

48. according to the described device unit of claim 43, wherein said spheric grain has from 1.0 to 1.5 length breadth ratio.

49. according to the described device unit of claim 43, wherein said spheric grain has from 1.0 to 1.2 length breadth ratio.

50. according to the described device unit of claim 43, wherein said spheric grain is a spherical resin particle.

51. according to the described device unit of claim 50, wherein said spherical resin particle utilizes inorganic fine powder to carry out surface treatment.

52. according to the described device unit of claim 50, wherein said spherical resin particle utilizes coupling agent to carry out surface treatment.

53. according to the described device unit of claim 43, wherein said resin particle is to have 3g/cm ³Or the conduction spheric grain of following real density.

54. according to the described device unit of claim 43, wherein said resin particle is to have 2.7g/cm ³Or the conduction spheric grain of following real density.

55. according to the described device unit of claim 43, wherein said resin particle is to have from 0.9g/cm ²To 2.5g/cm ³The conduction spheric grain of real density.

56. according to the described device unit of claim 53, wherein said conduction spheric grain has 10 ⁶Ω cm or following body resistivity.

57. according to the described device unit of claim 53, wherein said conduction spheric grain has from 10 ^-6Ω cm to 10 ³The body resistivity of Ω cm.

58. according to the described device unit of claim 53, wherein said conduction spheric grain comprises the spherical resin particle that was carbonized by sintering.

59. according to the described device unit of claim 53, wherein said conduction spheric grain comprises the spherical middle carbon microballon of being crossed by graphitization by sintering.

60. according to the described device unit of claim 53, the inside of wherein said conduction spheric grain was carbonized, its outside is by the graphitization mistake.

61. according to the described device unit of claim 60, wherein said conduction spheric grain is the spheric grain that obtains like this: the mesophase pitch that applies bulk on the surface of spherical resin particle, the coated particle of heating, sintering in inert atmosphere or vacuum then in oxidizing atmosphere.

62. according to the described device unit of claim 53, wherein said conduction spheric grain is coated with conducting metal or conducting metal oxide, or applies with both.

63. according to the described device unit of claim 53, wherein said conduction spheric grain comprises that its surface was carried out the spheric grain of conductive processing.

64. according to the described device unit of claim 63, wherein said conduction spheric grain is the spheric grain that obtains like this: conductive fine particle is sticked on the surface of spherical resin particle, and the particle of gained is carried out mechanical impact.

65. according to the described device unit of claim 53, wherein said conduction spheric grain comprises the spherical resin particle that wherein is scattered with conductive fine particle.

66. according to the described device unit of claim 65; wherein said conduction spheric grain is the particle that obtains like this: resin and conductive fine particle are mixed; the cooling of the mix products of gained is caused curing; with the cured product efflorescence of gained, and by mechanical treatment or thermal treatment or make the efflorescence product balling-up of gained by two kinds of processing.

67. according to the described device unit of claim 43, wherein said resinous coat contains resin particle, its amount is for from 2 parts of weight to 120 part weight, and is 100 parts with the weight of adhesive resin.

68. according to the described device unit of claim 43, wherein said quarternary ammonium salt compound comprises the compound of being represented by following general molecular formula:

Wherein, R ₁, R ₂, R ₃, R ₄In each represent alkyl, it can have substitute, aryl, it can have substitute, or aralkyl, it can have substitute, and can be identical or different; And X-represents negative ion.

69. according to the described device unit of claim 68, wherein said negative ion comprises select a kind of from following group: the organic sulfate ion, the organic sulfonic acid salt ion, the organic phosphoric acid salt ion, molybdate ion, tungstate ion contains the heteropoly acid ion of molybdenum atom and contains the heteropoly acid ion of tungsten atom.

70. according to the described device unit of claim 43, wherein said resinous coat contains described quarternary ammonium salt compound, its amount is for from 1 part of weight to 100 part weight, and is 100 parts with the weight of adhesive resin.

71. according to the described device unit of claim 43, wherein said adhesive resin has-NH ₂Base ,=the NH base and-in the NH-chain any one.

72. according to the described device unit of claim 71, the resin of wherein said adhesive resin for from the group that comprises following resin, selecting: phenol resin, polyamide and urethane resin.

73. according to the described device unit of claim 43, wherein said resinous coat has the center line surfaceness that scope is 0.2-3.5.

74. according to the described device unit of claim 43, the wherein said developer that fills positive electricity comprises the toner that can fill positive electricity.

75. according to the described device unit of claim 43, the wherein said developer that fills positive electricity is the one-pack type developer with the magnetic toner that can fill positive electricity.

76. according to the described device unit of claim 43, the wherein said developer that fills positive electricity is the one-pack type developer with the non-magnetic toner that can fill positive electricity.

77. according to the described device unit of claim 74, the wherein said toner that fills positive electricity comprises detackifier.

78. according to the described device unit of claim 74, the wherein said toner that fills positive electricity comprises positive charge control agent.

79. according to the described device unit of claim 74, the wherein said developer that fills positive electricity comprises toner that can fill positive electricity and the external additive that utilizes fluid lubricant to handle.

80. according to the described device unit of claim 74, the wherein said toner that fills positive electricity comprises its upper support the colorant of fluid lubricant or the magnetic powder that its upper support has fluid lubricant, perhaps has described colorant and magnetic powder.

81. according to the described device unit of claim 74, the wherein said toner that fills positive electricity has the average weight particle diameter in its particle size distribution be 3-12 μ m, and have 4.0 μ m or more the quantity content of the toner-particle of minor diameter be 30% or still less, the volume content with toner-particle of 12.7 μ m or larger diameter is 12.0% or still less.

82. according to the described device unit of claim 43, the thickness of the developer layer of the filled positive electricity that will form on described developer carrier wherein is less than the minimum clearance between the surface of the surface of described developer carrier and electrostatic latent image bearing part.

83. according to the described device unit of claim 43, comprising when developing, providing bias voltage to described developer carrier.

84. 3 described device units according to Claim 8, wherein said bias voltage has the AC bias that is superimposed with DC component on it.

85., wherein also comprise the electrostatic latent image supporting member that comprises as a unit according to the described device unit of claim 43.

86. an image forming method may further comprise the steps:

Wherein:

In described development step, make developing electrostatic latent image by means of developing apparatus, described developing apparatus comprises:

Described resinous principle contains (I) adhesive resin at least, and (II) Dao Dian fine powder (III) has the spheric grain of number average particle diameter from 0.3 μ m to 30 μ m, and the quarternary ammonium salt compound that (IV) can fill positive electricity to iron powder; And

The described developer that fills positive electricity by the friction between the surface of itself and developer carrier by frictional electrification, make to give positive triboelectric charge, and make developing electrostatic latent image by the developer that uses the filled positive electricity that has been given positive triboelectric charge for the developer that can fill positive electricity.

87. 6 described methods according to Claim 8, wherein said spheric grain has the number average particle diameter from 2 μ m to 20 μ m.

88. 6 described methods according to Claim 8, wherein said spheric grain has 3g/cm ³Or following real density.

89. 6 described methods according to Claim 8, wherein said spheric grain has 2.7g/cm ³Or following real density.

90. 6 described methods according to Claim 8, wherein said spheric grain has from 0.9g/cm ³To 2.5g/cm ³Real density.

91. 6 described methods according to Claim 8, wherein said spheric grain has from 1.0 to 1.5 length breadth ratio.

92. 6 described methods according to Claim 8, wherein said spheric grain has from 1.0 to 1.2 length breadth ratio.

93. 6 described methods according to Claim 8, wherein said spheric grain is a spherical resin particle.

94. according to the described method of claim 93, wherein said spherical resin particle utilizes inorganic fine powder to carry out surface treatment.

95. according to the described method of claim 93, wherein said spherical resin particle utilizes coupling agent to carry out surface treatment.

96. 6 described methods according to Claim 8, wherein said resin particle is to have 3g/cm ³Or the conduction spheric grain of following real density.

97. 6 described methods according to Claim 8, wherein said resin particle is to have 2.7g/cm ³Or the conduction spheric grain of following real density.

98. 6 described methods according to Claim 8, wherein said resin particle is to have from 0.9g/cm ²To 2.5g/cm ³The conduction spheric grain of real density.

99. according to the described method of claim 96, wherein said conduction spheric grain has 10 ⁶Ω cm or following body resistivity.

100. according to the described method of claim 96, wherein said conduction spheric grain has from 10 ^-6Ω cm to 10 ³The body resistivity of Ω cm.

101. according to the described method of claim 96, wherein said conduction spheric grain comprises the spherical resin particle that was carbonized by sintering.

102. according to the described method of claim 96, wherein said conduction spheric grain comprises the spherical middle carbon microballon of being crossed by graphitization by sintering.

103. according to the described method of claim 96, the inside of wherein said conduction spheric grain was carbonized, its outside is by the graphitization mistake.

104. according to the described method of claim 103, wherein said conduction spheric grain is the spheric grain that obtains like this: the mesophase pitch that applies bulk on the surface of spherical resin particle, the coated particle of heating, sintering in inert atmosphere or vacuum then in oxidizing atmosphere.

105. according to the described method of claim 96, wherein said conduction spheric grain is coated with conducting metal or conducting metal oxide, or applies with both.

106. according to the described method of claim 96, wherein said conduction spheric grain comprises that its surface was carried out the spherical resin particle of conductive processing.

107. according to the described method of claim 106, wherein said conduction spheric grain is the spheric grain that obtains like this: conductive fine particle is sticked on the surface of spherical resin particle, and the particle of gained is carried out mechanical impact.

108. according to the described method of claim 96, wherein said conduction spheric grain comprises the spherical resin particle that wherein is scattered with conductive fine particle.

109. according to the described method of claim 108; wherein said conduction spheric grain is the particle that obtains like this: resin and conductive fine particle are mixed; the cooling of the mix products of gained is caused curing; with the cured product efflorescence of gained, and by mechanical treatment or thermal treatment or make the efflorescence product balling-up of gained by two kinds of processing.

110. 6 described methods according to Claim 8, wherein said resinous coat contains resin particle, and its amount is for from 2 parts of weight to 120 part weight, and is 100 parts with the weight of adhesive resin.

111. 6 described methods according to Claim 8, wherein said quarternary ammonium salt compound comprises the compound of being represented by following general molecular formula:

112. according to the described method of claim 111, wherein said negative ion comprises select a kind of from following group: the organic sulfate ion, the organic sulfonic acid salt ion, the organic phosphoric acid salt ion, molybdate ion, tungstate ion contains the heteropoly acid ion of molybdenum atom and contains the heteropoly acid ion of tungsten atom.

113. 6 described methods according to Claim 8, wherein said resinous coat contains described quarternary ammonium salt compound, and its amount is for from 1 part of weight to 100 part weight, and is 100 parts with the weight of adhesive resin.

114. 6 described methods according to Claim 8, wherein said adhesive resin has-NH ₂Base ,=the NH base and-in the NH-chain any one.

115. according to the described method of claim 114, the resin of wherein said adhesive resin for from the group that comprises following resin, selecting: phenol resin, polyamide and urethane resin.

116. 6 described methods according to Claim 8, wherein said resinous coat has the center line surfaceness that scope is 0.2-3.5.

117. 6 described methods according to Claim 8, the wherein said developer that fills positive electricity comprises the toner that can fill positive electricity.

118. 6 described methods according to Claim 8, the wherein said developer that fills positive electricity is the one-pack type developer with the magnetic toner that can fill positive electricity.

119. 6 described methods according to Claim 8, the wherein said developer that fills positive electricity is the one-pack type developer with the non-magnetic toner that can fill positive electricity.

120. according to the described method of claim 117, the wherein said toner that fills positive electricity comprises detackifier.

121. according to the described method of claim 117, the wherein said toner that fills positive electricity comprises positive charge control agent.

122. 6 described methods according to Claim 8, the wherein said developer that fills positive electricity comprise the toner that can fill positive electricity and outsidely are added on this and can fill inorganic fine powder on the positive electricity toner.

123. according to the described method of claim 117, the wherein said toner that fills positive electricity comprises toner that can fill positive electricity and the external additive that utilizes fluid lubricant to handle

124. according to the described method of claim 117, it is 3-12 μ m that the wherein said toner that fills positive electricity has the average weight particle diameter, and have 4.0 μ m or more the quantity content of the particle size distribution of the toner-particle of minor diameter be 30% or still less, the volume content with toner-particle of 12.7 μ m or larger diameter is 12.0% or still less.

125. 6 described methods according to Claim 8, the thickness of the developer layer of the filled positive electricity that will form on described developer carrier wherein is less than the minimum clearance between the surface of the surface of described developer carrier and electrostatic latent image bearing part.

126. 6 described methods according to Claim 8 are comprising providing bias voltage so that developing electrostatic latent image in development step to described developer carrier.

127. according to the described method of claim 126, wherein said bias voltage has the AC bias that is superimposed with DC component on it.

128. 6 described methods according to Claim 8, wherein said latent image development part comprises the electronic photography photosensitive-member.